Method for forming a coating

Abstract

The present disclosure relates to coatings formed from tantalum-based precursors, and methods for forming and using such coatings. The coatings can be used as photopatternable or radiation-sensitive coatings. In non-limiting embodiments, the radiation can include extreme ultraviolet (EUV) or deep ultraviolet (DUV) radiation.

Description

[Technical Field]

[0001] [Incorporated by reference] A PCT application has been filed contemporaneously herewith as part of the present application. Each application to which this application claims benefit or priority, as identified in the contemporaneous PCT application, is incorporated herein by reference in its entirety for all purposes. This application claims the benefit of U.S. Provisional Patent Application No. 62 / 705,853, filed July 17, 2020, which is incorporated herein by reference in its entirety.

[0002] The present disclosure relates to coatings formed from tantalum-based precursors, and methods for forming and using such coatings. The coatings can be used as photopatternable coatings or radiation-sensitive coatings. In non-limiting embodiments, the radiation can include extreme ultraviolet (EUV) radiation or deep ultraviolet (DUV) radiation. [Background technology]

[0003] The background discussion provided herein is intended to generally present the state of the art, and no admission is made, expressly or impliedly, that the work of the inventors named herein, as well as aspects of the present specification that may not otherwise be recognized as prior art at the time of filing, is prior art to the present technology, even though they are described in this background section.

[0004] Patterning thin films in semiconductor processing is often a critical step in semiconductor manufacturing. Patterning involves lithography. In photolithography, such as 193 nm photolithography, patterns are printed by emitting photons from a photon source onto a mask, printing the pattern onto a light-sensitive photoresist, which causes a chemical reaction in the photoresist that, after development, removes certain portions of the photoresist to form the pattern.

[0005] Advanced technology nodes (as defined by the International Technology Roadmap for Semiconductors) include 22 nm, 16 nm, and finer nodes. For example, at the 16 nm node, the width of a typical via or line in a damascene structure is typically about 30 nm or less. The shrinking features of advanced semiconductor integrated circuits (ICs) and other devices require improved lithographic resolution.

[0006] Extreme ultraviolet (EUV) lithography can extend lithography technology by moving to shorter imaging light source wavelengths than thought achievable with other photolithography methods. EUV light sources with wavelengths of approximately 10-20 nm or 11-14 nm, e.g., 13.5 nm, can be used in cutting-edge lithography tools, also known as scanners. EUV radiation is strongly absorbed by a wide range of solid and fluid materials, including quartz and water vapor, and therefore can be operated in a vacuum. Summary of the Invention

[0007] The present disclosure relates to the use of tantalum (Ta)-based precursors to provide patterned radiation-sensitive films (e.g., EUV-sensitive films). In one embodiment, the Ta-based precursor is an EUV-active organotantalum compound that can be used alone to deposit a photoresist (PR) film. Alternatively, the Ta-based precursor is used in conjunction with another organometallic compound (e.g., an organotin compound) to provide a mixed-metal EUV-sensitive PR film. Such films can be vapor-deposited and wet- or dry-developable.

[0008] Tantalum nitride (TaN) is a widely used hard mask during semiconductor processing, primarily due to its mechanical stability, and its high EUV absorption, which allows it to be used as an absorber in EUV lithography masks. As used herein, TaN includes TaN, Ta2N, Ta3N5, Ta4N5, Ta4N, Ta5N6, and Ta6N 2.5 It refers to any useful stoichiometric composition, including, but not limited to, ...

[0009] Thus, in one non-limiting example, the Ta-based precursor herein may be an organic tantalum nitrogen-containing compound that can in turn provide a TaN-based PR film. Such TaN-based PRs can exhibit enhanced stability, thereby providing thicker PR films, and can withstand harsh development chemicals that might otherwise damage tin (Sn)-only PR films, and / or resist etching chemicals that might otherwise damage Sn-only PR films. Furthermore, such Ta-based precursors enable photopatterning of the film, thereby facilitating the use of such Ta-based films as patterned hard masks.

[0010] In a first aspect, the invention features a stack including a semiconductor substrate having an upper surface; and a patterned radiation-sensitive coating disposed on the upper surface of the semiconductor substrate, where the coating includes Ta. In other embodiments, the coating further includes Sn. In still other embodiments, the coating further includes nitrogen (N). In some embodiments, the coating includes tantalum nitride and / or tin oxide.

[0011] In some embodiments, the patterned radiation-sensitive coating comprises a mixed organometallic coating comprising Ta and Sn. In other embodiments, the coating comprises a tantalum-containing layer disposed on the top or bottom surface of a Sn-containing layer. In yet other embodiments, the coating comprises multiple alternating Ta-containing and tin-containing layers. Non-limiting examples of the Ta-containing layer include tantalum nitride, and non-limiting examples of the Sn-containing layer include organotin oxide.

[0012] In a second aspect, the disclosure features a method (e.g., to form a coating) that includes depositing a Ta-based precursor on a surface of a substrate to provide a patterned radiation-sensitive coating, the Ta-based precursor including a patterned radiation-sensitive moiety. In some embodiments, the patterned radiation-sensitive moiety of the Ta-based precursor includes an EUV-labile group. In other embodiments, the patterned radiation-sensitive moiety of the Ta-based precursor includes an imide group.

[0013] In some embodiments, the Ta-based precursor has the formula (I): TaR b L c (I) and wherein each R is independently an EUV-labile group, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted imino, or optionally substituted alkylene; each L is independently a ligand or other moiety that is reactive with a reducing gas or an alkyne; b≧0; and c≧1.

[0014] In other embodiments, the Ta-based precursor has the formula (IA): R=Ta(L) b (IA) and In the formula, R=NR i or =CR i R ii each L is independently halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or a divalent ligand bonded to Ta, wherein the divalent ligand is —NR i -Ak-NR ii - and each R i and R iiare independently H, optionally substituted linear alkyl, optionally substituted branched alkyl, or optionally substituted cycloalkyl; Ak is optionally substituted alkylene or optionally substituted alkenylene; and b≧1.

[0015] In some embodiments, the deposition further includes an organometallic compound. In other embodiments, the Ta-based precursor and the organometallic compound may be deposited together or sequentially in a sequence (e.g., in alternating cycles). In some embodiments, the deposition further includes adjusting the relative amounts of the Ta-based precursor and the organometallic compound deposited in the film. In other embodiments, the adjustment includes changing the flow rates and / or deposition time of the tantalum-based precursor and the organometallic compound.

[0016] In some embodiments, the deposition further comprises a Ta-based precursor and an organometallic compound deposited sequentially in a sequence. In certain embodiments, the sequence comprises depositing a Ta-based precursor followed by or preceding an organometallic compound. In other embodiments, the deposition further comprises adjusting the number or order of the sequence of the Ta-based precursor and the subsequent or preceding organometallic compound.

[0017] In certain embodiments, the deposition comprises depositing a Ta-based precursor and an organometallic compound, optionally in the presence of a reducing gas or an alkyne, thereby resulting in a patterned radiation-sensitive coating comprising a mixed organometallic coating having two or more different metals. In some embodiments, the organometallic compound comprises a Sn-based precursor, and the mixed organometallic coating comprises Ta and Sn. In certain embodiments, the film formation is performed at a temperature below about 250°C, below about 100°C, or from 0°C to about 250°C (e.g., 0°C to 50°C, 0°C to 80°C, 0°C to 90°C, 0°C to 95°C, 10°C to 50°C, 10°C to 80°C, 10°C to 90°C, 10°C to 95°C, 10°C to 100°C, 10°C to 130°C, 10°C to 150°C, 10°C to 180°C, 10°C to 200°C, 20°C to 50°C, 20°C to 80°C, 20°C to 90°C, 20°C to 95°C, 20°C to 100°C, 20°C to 130°C, 20°C to 150°C, 20°C to 180°C, 20°C to 200°C, The method includes depositing a film by chemical vapor deposition (CVD) at a temperature of 0°C, 20°C to 230°C, 20°C to 250°C, 25°C to 50°C, 25°C to 80°C, 25°C to 90°C, 25°C to 95°C, 25°C to 100°C, 25°C to 130°C, 25°C to 150°C, 25°C to 180°C, 25°C to 200°C, 25°C to 230°C, 25°C to 250°C, 30°C to 50°C, 30°C to 80°C, 30°C to 90°C, 30°C to 95°C, 30°C to 100°C, 30°C to 130°C, 30°C to 150°C, 30°C to 180°C, 30°C to 200°C, 30°C to 230°C, or 30°C to 250°C. In certain embodiments, the CVD deposition is carried out at a lower temperature to ensure retention of the EUV sensitive moieties in the coating.

[0018] In other embodiments, the deposition includes depositing a metalorganic compound in a chamber, optionally in the presence of a counter reactant, to provide a metalorganic-containing layer; purging the chamber with a purge gas (e.g., an inert gas such as any described herein); depositing a Ta-based precursor in the chamber, to provide a Ta-containing layer disposed on an upper surface of the metalorganic-containing layer; purging the chamber with another purge gas (e.g., an inert gas such as any described herein); and exposing the Ta-containing layer to a reducing gas or an alkyne. In some embodiments, the metalorganic compound includes a Sn-based precursor, and the metalorganic-containing layer includes Sn. In certain embodiments, the deposition includes deposition by atomic layer deposition.

[0019] In some embodiments, the organometallic compound has the formula (II): M a R b L c (II) and wherein M is a metal (e.g., any described herein); each R is independently an EUV-labile ligand, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is independently a ligand, ion, or other moiety reactive with a counter reactant, and R and L together with M can optionally form a heterocyclyl group, or R and L together can optionally form a heterocyclyl group; a≧1; b≧1; c≧1. In other embodiments, R is an optionally substituted alkyl and M is tin. In still other embodiments, each L is independently H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy.

[0020] In other embodiments, the deposition further comprises one or more counter reactants, non-limiting examples of which include oxygen-containing counter reactants, including O2, O3, water, peroxide, hydrogen peroxide, oxygen plasma, water plasma, alcohols, dihydroxy alcohols, polyhydroxy alcohols, fluorinated dihydroxy alcohols, fluorinated polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, and combinations thereof.

[0021] In some embodiments, the deposition further comprises a reducing gas, hydrogen gas, or an alkyne. Non-limiting reducing gases and alkynes include hydrogen (H), amines (NH), trialkylamines (e.g., NR, where each R is independently an optionally substituted alkyl), and acetylene.

[0022] In a third aspect, the present disclosure encompasses a method (e.g., for use in a resist) comprising depositing a Ta-based precursor on a surface of a substrate to provide a patterned radiation-sensitive film as a resist film; patterning the resist film by exposing it to patterning radiation to provide an exposed film having radiation-exposed and radiation-unexposed regions; and developing the exposed film to remove the radiation-exposed regions to provide a pattern in a positive-tone resist film or remove the radiation-unexposed regions to provide a pattern in a negative-tone resist. In some embodiments, the deposition comprises the use of a counter reactant (e.g., an oxygen-containing counter reactant such as any described herein).

[0023] In some embodiments, the method includes patterning the photoresist layer (e.g., after deposition) with EUV exposure, thereby resulting in an exposed film having EUV-exposed and EUV-unexposed regions. In some embodiments, the photoresist layer underlies a capping layer. In other embodiments, the EUV radiation has a wavelength in the range of about 10 nm to about 20 nm in a vacuum environment.

[0024] In some embodiments, the development includes dry or wet development chemicals. In certain embodiments, the dry development chemicals include one or more halide or other gases (e.g., HCl, HBr, HI, HF, Cl, Br, BCl, BF, NF, NH, SOCl, SF, CF, CHF, CHF, and CHF, and combinations thereof with N and O, etc.), optionally provided as a plasma. In other embodiments, the wet development chemicals include organic developers such as ketones (e.g., 2-heptanone, cyclohexanone, or acetone), esters (e.g., γ-butyrolactone, n-butyl acetate, or ethyl 3-ethoxypropionate (EEP)), alcohols (e.g., isopropyl alcohol (IPA)), or ethers such as glycol ethers (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA)), and combinations thereof.

[0025] In a fourth aspect, the present disclosure features an apparatus for forming a resist film. In some embodiments, the apparatus includes a deposition module, a patterning module, a development module, and a controller including one or more memory elements, one or more processors, and system control software encoded with instructions, including machine-readable instructions.

[0026] In some embodiments, the deposition module comprises a chamber for depositing a patterned radiation-sensitive film (e.g., an EUV-sensitive film). In other embodiments, the patterning module comprises a photolithography tool having a source of sub-300 nm wavelength radiation (e.g., the source may be a source of sub-30 nm wavelength radiation). In yet other embodiments, the development module comprises a chamber for developing a resist film.

[0027] In some embodiments, the instructions include machine-readable instructions for causing deposition (e.g., in a deposition module) of a Ta-based precursor including a patterned radiation-sensitive moiety onto an upper surface of a semiconductor substrate to form a patterned radiation-sensitive film as a resist film.

[0028] In further embodiments, the instructions include machine-readable instructions (e.g., in a deposition module) for causing further deposition of the organometallic compound in the optional presence of a reducing gas, an alkyne, and / or a counter reactant. In certain embodiments, a Ta-based precursor and an organometallic compound are deposited together to provide a mixed organometallic film having two or more different metals. In some embodiments, the resist film comprises a mixed organometallic film containing both Ta and Sn. In other embodiments, a Ta-based precursor and an organometallic compound are deposited in alternating cycles to provide an organometallic-containing layer and a Ta-containing layer disposed on top of the organometallic-containing layer. In some embodiments, the resist film comprises multiple Ta-containing and Sn-containing layers.

[0029] In some embodiments, the instructions include machine-readable instructions for causing (e.g., in a patterning module) directly patterning the resist coating with patterning radiation exposure (e.g., with EUV exposure) at sub-300 nm resolution (e.g., or sub-30 nm resolution), thereby forming an exposed coating having radiation-exposed and radiation-unexposed regions. In other embodiments, the exposed coating has EUV-exposed and EUV-unexposed regions. In yet other embodiments, the instructions include machine-readable instructions for causing (e.g., in a development module) developing the exposed coating to remove the radiation-exposed or radiation-unexposed regions, resulting in a pattern in the resist coating. In certain embodiments, the machine-readable instructions include instructions for causing removal of the EUV-exposed or EUV-unexposed regions.

[0030] In any embodiment herein, the patterned radiation sensitive coating comprises an extreme ultraviolet (EUV) sensitive coating, a deep ultraviolet (DUV) sensitive coating, a photoresist coating, or a photopatternable coating.

[0031] In any embodiment herein, the patterned radiation sensitive coating comprises an organometallic material, an organometallic oxide material, a tantalum nitride material, a tin oxide material, and / or an organotin oxide material.

[0032] In any embodiment herein, the patterned radiation-sensitive coating has a thickness of about 5 nm to about 50 nm (e.g., about 5 nm to 10 nm, 5 nm to 20 nm, 5 nm to 30 nm, 5 nm to 40 nm, 8 nm to 20 nm, 8 nm to 30 nm, 8 nm to 40 nm, 8 nm to 50 nm, 10 nm to 20 nm, 10 nm to 30 nm, 10 nm to 40 nm, or 10 nm to 50 nm).

[0033] In any embodiment herein, the Ta-based precursor comprises a structure having formula (I) or (IA) described herein.

[0034] In any embodiment herein, the organometallic compound comprises a structure having formula (II), (II-A), (III), (IV), (V), (VI), (VII), (VIII), or (IX) described herein.

[0035] In any embodiment herein, the deposition includes providing or depositing a Ta-based precursor and / or an organometallic compound in vapor form. In other embodiments, the deposition includes providing a reducing gas, a hydrocarbon, an alkyne, and / or a counter reactant in vapor form. In certain embodiments, the deposition includes chemical vapor deposition (CVD), atomic layer deposition (ALD), or molecular layer deposition (MLD), and plasma-enhanced forms thereof.

[0036] In any embodiment herein, depositing the Ta-based precursor further comprises providing a reducing gas, a hydrocarbon, or an alkyne. In some embodiments, the alkyne is acetylene.

[0037] In any embodiment herein, depositing the organometallic compound further includes providing a counter reactant, non-limiting examples of which include oxygen-containing counter reactants including O, O, water, peroxide, hydrogen peroxide, oxygen plasma, water plasma, alcohols, dihydroxy alcohols, polyhydroxy alcohols, fluorinated dihydroxy alcohols, fluorinated polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, and combinations thereof.

[0038] In any embodiment herein, the method further includes purging the chamber with a purge gas (e.g., an inert gas or carrier gas, such as argon (Ar), nitrogen (N), oxygen (O), ambient air, or a mixture thereof) after depositing the Ta-based precursor or organometallic compound. Additional details are provided below.

[0039] definition As used interchangeably herein, "acyloxy" or "alkanoyloxy" refers to an acyl group or an alkanoyl group, as defined herein, attached to the parent molecular group through an oxy group. In certain embodiments, the alkanoyloxy is -OC(O)-Ak, where Ak is an alkyl group, as defined herein. In some embodiments, the unsubstituted alkanoyloxy is C 2~7 Alkanoyloxy groups. Exemplary alkanoyloxy groups include acetoxy.

[0040] "Alkenyl" refers to an optionally substituted C alkyl group having one or more double bonds. 2~24 The alkenyl group is a cyclic group (e.g., C 3~24 The alkenyl group may be substituted or unsubstituted. For example, an alkenyl group may be substituted with one or more of the substituents described herein for alkyl.

[0041] "Alkenylene" refers to an optionally substituted C 2~24 It refers to the polyvalent (e.g., divalent) form of an alkenyl group, which is an alkyl group. An alkenylene group is a cyclic (e.g., C 3~24 The alkenylene group may be substituted or unsubstituted. For example, the alkenylene group may be substituted with one or more substituents described herein for alkyl. Exemplary non-limiting alkenylene groups include -CH=CH- or -CH=CHCH2-.

[0042] "Alkoxy" means -OR, where R is an optionally substituted alkyl group as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, trihaloalkoxy such as trifluoromethoxy, and the like. Alkoxy groups can be substituted or unsubstituted. For example, an alkoxy group can be substituted with one or more substituents as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C 1~3 , C 1~6 , C 1~12 , C 1~16 , C 1~18 , C 1~20 , or C 1~24 Examples include alkoxy groups.

[0043] The terms "alkyl" and "alk" refer to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), cyclopropyl, n-butyl (n-Bu), isobutyl (i-Bu), s-butyl (s-Bu), t-butyl (t-Bu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, and tetracosyl. An alkyl group can be cyclic (e.g., C 3~24The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may include a haloalkyl, in which the alkyl group is substituted with one or more halo groups, as described herein. In another example, the alkyl group may be substituted with one, two, three, or, in the case of alkyl groups of two or more carbons, four substituents independently selected from the group consisting of: (1) C 1~6 Alkoxy (e.g., —O-Ak, where Ak is an optionally substituted C 1~6 (2) amino (e.g., —NR N1 R N2 where R N1 and R N2 each independently is H or optionally substituted alkyl, or R N1 and R N2 each taken together with the nitrogen atom to which it is attached forms a heterocyclyl group; (3) aryl; (4) arylalkoxy (e.g., -O-Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl); (5) aryloyl (e.g., -C(O)-Ar, where Ar is an optionally substituted aryl); (6) cyano (e.g., -CN); (7) carboxaldehyde (e.g., -C(O)H); (8) carboxyl (e.g., -COH); (9) C 3~8 Cycloalkyl (e.g., monovalent saturated or unsaturated non-aromatic cyclic C 3~8(10) halo (e.g., F, Cl, Br, or I); (11) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms such as nitrogen, oxygen, phosphorous, sulfur, or halo, unless otherwise specified); (12) heterocyclyloxy (e.g., -O-Het, where Het is heterocyclyl as described herein); (13) heterocyclyloyl (e.g., -C(O)-Het, where Het is heterocyclyl as described herein); (14) hydroxyl (e.g., -OH); (15) N-protected amino; (16) nitro (e.g., -NO); (17) oxo (e.g., =O); (18) -COR A (In the formula, R A is (a)C 1~6 Alkyl, (b) C 4~18 aryl, and (c) (C 4~18 Aryl)C 1~6 alkyl (e.g., -Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (19) -C(O)NR B R C (In the formula, R B and R C each independently being (a) hydrogen, (b) C 1~6 Alkyl, (c) C 4~18 aryl, and (d) (C 4~18 Aryl)C 1~6 alkyl (e.g., -Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); and (20) -NR G R H (In the formula, R G and R H each of which is independently (a) hydrogen, (b) an N-protecting group, (c) C 1~6 Alkyl, (d) C 2~6 alkenyl (e.g., optionally substituted alkyl having one or more double bonds); (e) C 2~6Alkynyl (e.g., optionally substituted alkyl having one or more triple bonds), (f) C 4~18 Aryl, (g) (C 4~18 Aryl)C 1~6 alkyl (e.g., Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (h) C 3~8 cycloalkyl, and (i) (C 3~8 Cycloalkyl)C 1~6 alkyl (e.g., -Lk-Cy, where Lk is a divalent form of an optionally substituted alkyl group and Cy is an optionally substituted cycloalkyl as described herein), and in one embodiment, the two groups are not attached to the nitrogen atom through a carbonyl group, (C 3~8 Cycloalkyl)C 1~6 Alkyl. The alkyl group may be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is C 1~3 , C 1~6 , C 1~12 , C 1~16 , C 1~18 , C 1~20 , or C 1~24 It is an alkyl group.

[0044] "Alkylene" refers to the polyvalent (e.g., divalent) form of an alkyl group as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, an alkylene group is a C 1~3 , C 1~6 , C 1~12 , C 1~16 , C 1~18 , C 1~20 , C 1~24 , C 2~3 , C 2~6 , C 2~12 , C 2~16 , C 2~18 , C 2~20 , or C 2~24It is an alkylene group. The alkylene group may be branched or unbranched. Also, the alkylene group may be substituted or unsubstituted. For example, the alkylene group may be substituted with one or more substituents described herein for alkyl.

[0045] "Alkynyl" refers to an optionally substituted C alkyl group having one or more triple bonds. 2~24 It refers to an alkyl group. Alkynyl groups can be cyclic or acyclic, and are exemplified by ethynyl, 1-propynyl, and the like. Alkynyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more substituents described herein for alkyl.

[0046] "Amino" is -NR N1 R N2 where R N1 and R N2 each is independently H, optionally substituted alkyl, or optionally substituted aryl, or R N1 and R N2 taken together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein.

[0047] "Aryl" refers to any carbon-based aromatic group, including, but not limited to, phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, and terphenyl, and includes fused benzo-C groups such as indanyl, tetrahydronaphthyl, and fluorenyl. 4~8Cycloalkyl radicals (e.g., as defined herein) are included. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group having at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl is included within the term aryl and defines a group containing an aromatic group that does not contain a heteroatom. Aryl groups may be substituted or unsubstituted. Aryl groups may be substituted with 1, 2, 3, 4, or 5 substituents, such as any of those described herein for alkyl.

[0048] "Arylene" refers to a polyvalent (e.g., divalent) form of an aryl group as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenylether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, an arylene group is C 4~18 , C 4~14 , C 4~12 , C 4~10 , C 6~18 , C 6~14 , C 6~12 , or C 6~10 It is an arylene group. The arylene group may be branched or unbranched. The arylene group may also be substituted or unsubstituted. For example, the arylene group may be substituted with one or more substituents described herein for alkyl or aryl.

[0049] "Carbonyl" means the group -C(O)-, which also can be depicted as >C=O.

[0050] "Cycloalkenyl," unless otherwise specified, means a monovalent unsaturated non-aromatic or aromatic cyclic hydrocarbon group of 3 to 8 carbons having one or more double bonds. Cycloalkenyl groups can also be substituted or unsubstituted. For example, cycloalkenyl groups can be substituted with one or more groups, including those described herein for alkyl.

[0051] "Cycloalkyl," unless otherwise specified, means a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group of 3 to 8 carbons, exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.]heptyl, and the like. Cycloalkyl groups can also be substituted or unsubstituted. For example, cycloalkyl groups can be substituted with one or more groups, including those described herein for alkyl.

[0052] "Halo" means F, Cl, Br, or I.

[0053] "Haloalkyl" means an alkyl group, as defined herein, that is substituted with one or more halo.

[0054] "Heteroalkyl" means an alkyl group, as defined herein, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, selenium, or halo).

[0055] "Heteroalkylene" means a divalent form of an alkylene group, as defined herein, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, selenium, or halo). Heteroalkylene groups can also be substituted or unsubstituted. For example, heteroalkylene groups can be substituted with one or more substituents described herein for alkyl.

[0056] "Heterocyclyl," unless otherwise indicated, refers to a 3-, 4-, 5-, 6-, or 7-membered ring (e.g., a 5-, 6-, or 7-membered ring) containing 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, selenium, or halo). 3-membered rings have zero to one double bond, 4- and 5-membered rings have zero to two double bonds, and 6- and 7-membered rings have zero to three double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, and benzothienyl. Heterocycles include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothia ... benzoisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl,Benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl , benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazepam, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl,Dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroypyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxiranyl, dioxenyl, di Oxynyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl, isopropyl, ... Satyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazolyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidinyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthoindazolyl, naphthiindolyl, naphthiridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl, naphthyridinyl, octahydroisoquinolinyl oxacycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanoyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl,Phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyrronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl aryl, pyrrolizidinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyrrolid ... nyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianil, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thiethyl, thiiranyl, thiocanyl hiocanyl), thiochromanonyl, thiochromanil, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, urisyl, uridinyl, xanthenyl, xanthinyl,and xanthionyl, etc., as well as modified forms thereof (e.g., containing one or more oxo and / or amino groups) and salts thereof. Heterocyclyl groups can be substituted or unsubstituted. For example, heterocyclyl groups can be substituted with one or more of the substituents described herein for aryl.

[0057] "Hydroxyl" means --OH.

[0058] "Imino" means -NR-, where R can be H or optionally substituted alkyl.

[0059] "Oxo" means the radical =O.

[0060] As used herein, the term "about" means + / - 10% of any stated value. As used herein, the term modifies any stated value, range of values, or the endpoints of one or more ranges.

[0061] As used herein, "top," "bottom," "upper," "lower," "above," and "below" are used to provide relative relationships between structures. The use of these terms does not indicate or require that a particular structure be located in a particular position on the device.

[0062] Other features and advantages of the invention will be apparent from the following description and claims. [Brief explanation of the drawings]

[0063] [Figure 1A] 1A shows a schematic diagram of exemplary precursors and other reagents for film formation. A reaction is provided to provide a TaN-based PR film, including a non-limiting Ta-based precursor (Ta(=Nt-Bu)(NMe2)3) with a reducing gas (e.g., H2 or NH3). [Figure 1B]1B shows a schematic diagram of exemplary precursors and other reagents for film deposition. Further reactions are provided to provide mixed organometallic films containing Ta and Sn in the presence of a non-limiting Sn-based precursor (Sn(iPr)(NMe2)3).

[0064] [Figure 2] 2 shows a schematic diagram of exemplary precursors and other reagents for providing layered coatings. Cycle A provides a reaction for providing a SnO-based layer, including a non-limiting Sn-based precursor (Sn(iPr)(NMe2)3) with a counter reactant (e.g., HO), and cycle B provides a reaction for providing a TaN-based layer, including a non-limiting Ta-based precursor (Ta(=Nt-Bu)(NMe2)3) with a reducing gas (e.g., H2 or NH3). Alternating cycles A and B can form layered coatings.

[0065] [Figure 3A] 3A shows a diagram of a non-limiting method of using a Ta-based precursor during deposition. A block diagram of an exemplary method 300 including depositing a Ta-based precursor is provided. [Figure 3B] 3B shows a diagram of a non-limiting method of using a Ta-based precursor during deposition. A block diagram of another exemplary method 320 is provided that includes depositing a Ta-based precursor along with a Sn-based precursor. [Figure 3C] 3C shows a diagram of a non-limiting method of using a Ta-based precursor during deposition. A block diagram of yet another exemplary method 340 is provided that includes depositing a Ta-based precursor and an Sn-based precursor in alternating cycles.

[0066] [Figure 4] FIG. 4 shows a schematic diagram of an embodiment of a processing station 400 for dry development.

[0067] [Figure 5] FIG. 5 shows a schematic diagram of an embodiment of a multi-station processing tool 500 .

[0068] [Figure 6] FIG. 6 shows a schematic diagram of an embodiment of an inductively coupled plasma device 600 .

[0069] [Figure 7] FIG. 7 shows a schematic diagram of an embodiment of a semiconductor processing cluster tool architecture 700 . DETAILED DESCRIPTION OF THE INVENTION

[0070] The present disclosure relates generally to the field of semiconductor processing. In particular, the present disclosure relates to the use of Ta-based precursors during deposition. Such Ta-based precursors can provide deposited Ta-containing films that can exhibit enhanced EUV sensitivity and / or mechanical stability.

[0071] Current CVD-processable EUV PR films include low-density Sn-based films with limited mechanical stability. The soft chemistry of such Sn-based PR films can lead to reduced mechanical stability, which limits how thick a pre-developed PR layer can be before collapsing printed features. Furthermore, the mechanical instability of Sn-based PR films can restrict wet or dry development to less aggressive chemistries, which can limit opportunities for patterning optimization. By incorporating Ta-based precursors into such films, enhanced structural stability of pure Ta or mixed Ta / Sn films can be observed. Furthermore, EUV sensitivity can be enhanced by increasing the density of EUV-absorbing Ta atoms within the film.

[0072] Reference is made in detail herein to specific embodiments of the present disclosure. Examples of specific embodiments are illustrated in the accompanying drawings. While the present disclosure will be described in conjunction with such specific embodiments, it will be understood that it is not intended to limit the disclosure to such specific embodiments. Rather, it is intended to cover alternatives, modifications, and equivalents which may be included within the spirit and scope of the present disclosure. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. The present disclosure may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail in order to not unnecessarily obscure the present disclosure.

[0073] In EUV lithography, a patterned EUV resist is used to form a mask for use in etching the underlying layer. The EUV resist may be a polymer-based chemically amplified resist (CAR) produced by a liquid-based spin-on technique. An alternative to CAR is a directly photopatternable metal oxide-containing coating, such as those available from Inpria Corp. (Corvallis, Oregon), for example, as described in U.S. Patent Application Publication Nos. 2017 / 0102612, 2016 / 0216606, and 2016 / 0116839. These documents are incorporated herein by reference, at least with respect to the disclosure of photopatternable metal oxide-containing coatings. Such coatings may be produced by spin-on techniques or dry deposition. Metal oxide-containing films can be patterned directly (i.e., without the use of a separate photoresist) by EUV exposure in a vacuum environment providing sub-30 nm patterning resolution, as described, for example, in U.S. Pat. No. 9,996,004, entitled EUV PHOTOPATTERNING OF VAPOR-DEPOSITED METAL OXIDE-CONTAINING HARD MASKS, which issued on June 12, 2018, and / or International Application No. PCT / US19 / 31618, entitled METHODS FOR MAKING EUV PATTERNABLE HARD MASKS, which filed on May 9, 2019, and published as WO 2019 / 217749. The disclosures of these documents, at least regarding the composition, deposition, and patterning of directly photopatternable metal oxide films to form EUV resist masks, are incorporated herein by reference. Generally, patterning involves exposing the EUV resist to EUV radiation to form a light pattern in the resist, followed by development to remove portions of the resist according to the light pattern to form a mask.

[0074] Directly photopatternable EUV or DUV resists may be composed of or include metals and / or metal oxides mixed within an organic component. Metals / metal oxides hold great promise in that they can enhance EUV or DUV photon absorption, generate secondary electrons, and / or exhibit increased etch selectivity relative to underlying film stacks and device layers.

[0075] In general, resists can be used as either positive or negative resists by controlling the resist chemistry and / or the solubility or reactivity of the developer. It would be beneficial to have an EUV or DUV resist that can function as either a negative or positive resist. The present disclosure encompasses the use and development of the coating as either a negative or positive resist.

[0076] Methods for using Ta-based precursors The present disclosure generally includes any useful methods of using the Ta-based precursors described herein, which can include any useful lithography processes, deposition processes, radiation exposure processes, development processes, and post-application processes described herein.

[0077] In particular, tantalum-based precursors can include patterning radiation-sensitive moieties. Such moieties can be double-bonded ligands that can function as EUV-labile groups. As shown in Figure 1A, a non-limiting Ta-based precursor (Ta(=Nt-Bu)(NMe2)3) can be provided in the presence of a reducing gas (e.g., H2 or NH3) to provide a TaN-based PR film, which can be further exposed to EUV and developed (e.g., by dry development with Cl2 and plasma).

[0078] In certain embodiments, deposition of Ta-based PR films using only a single precursor can be performed by CVD. Such films exhibit certain attributes, such as improved mechanical stability of the resulting PR, allowing for more aggressive wet and dry development chemistries, thus leading to improved patterning quality. Such films may also allow for EUV sensitivity similar to Sn-based PR. Furthermore, such films can be patterned and developed with negative chemistries to yield a TaN hard mask, which could reduce the number of etching steps for the complete stack process.

[0079] Mixed-metal films can also be formed by incorporating other metal precursors. As shown in FIG. 1B, a non-limiting Ta-based precursor (Ta(=Nt-Bu)(NMe2)3) is provided in the presence of a reducing gas (e.g., H2 or NH3) and an organometallic compound, such as a Sn-based precursor (Sn(i-Pr)(NMe2)3). Deposition yields a mixed-metal (Ta / Sn) film with Ta-N bonds and EUV-labile ligands provided by the double-bonded ligands of the Ta-based precursor and the i-Pr group of the Sn-based precursor. This mixed-metal film can be further exposed to EUV and developed (e.g., by dry development with HBr followed by Cl2 plasma). Additional non-limiting Ta-based precursors and other metal precursors are described herein.

[0080] The deposition can be performed simultaneously or sequentially. As seen in FIG. 1B, Ta-based precursors and Sn-based precursors can be deposited simultaneously to provide a mixed metal coating. Alternatively, the precursors can be provided in cycles, as shown in FIG. 2, whereby cycle A is performed, followed by cycle B to deposit alternating Sn- and Ta-containing layers. Optionally, a purge step can be performed between cycles A and B.

[0081] In certain embodiments, simultaneous deposition of mixed-metal Sn- and Ta-based PR films can be performed by CVD or ALD. Such films exhibit certain attributes, such as a reduced density of EUV-sensitive portions of the PR, resulting in increased PR EUV sensitivity; and improved mechanical stability of the resulting PR, which may allow for more aggressive wet and dry development chemistries and therefore improved patterning quality. Such films may also allow for thicker PR layers, allowing the patterned and developed PR to serve as an etching hard mask, thereby reducing the number of etching steps for complete stack processing. Such mixed-metal films can have any useful combination and arrangement of Ta-, Sn-, and mixed Ta / Sn-containing layers within the stack, as well as gradient films with increasing EUV absorption with proximity to the substrate. In one example, a Ta-containing layer is used as a capping layer, and / or a Sn-containing layer is closer to the substrate. In another example, the stack includes a lower Sn-containing layer, an upper Ta-containing layer, and an intermediate Ta / Sn-containing layer disposed between the lower and upper layers. In yet another example, any of the coatings and layers of Figures 1A-1B and 2 can be combined in a stack.

[0082] 3A-3C provide flowcharts of exemplary methods having various operations, including optional operations. In any of the methods herein, optional steps may be performed to further condition, modify, or treat the EUV-sensitive coating, substrate, photoresist layer, and / or capping layer.

[0083] 3A illustrates an exemplary method 302 using a Ta-based precursor. As can be seen, in operation 302, a film is deposited using a Ta-based precursor that may optionally include the presence of a reducing gas, a hydrocarbon, an alkyne, or some combination thereof.

[0084] If only Ta-based precursors are used, the resulting film can comprise a pure Ta-based PR film. Such a film can form TaN upon exposure to EUV photons, which will act as a negative PR, resulting in patterns with high mechanical stability and resistance to development chemicals. Ta-based PR can be easily removed by CVD or ALD processes using reducing gases (e.g., H2, NH3, NR3). N1 R N2 R N3 where R N1 , R N2 , and R N3 wherein each independently is an optionally substituted alkyl, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-butyl, etc.), can be used to partially react a Ta precursor, such that the resulting Ta-based film contains some EUV-labile organic moieties.

[0085] In optional operation 304, the backside surface or bevel of the substrate may be cleaned and / or the edge bead of photoresist deposited in a previous step may be removed. Such cleaning or removal steps may be useful for removing particles that may be present after deposition of the photoresist layer. The removal step may include treating the wafer with a wet metal oxide (MeOx) edge bead removal (EBR) step.

[0086] In another example, the method can include optional operation 306 of performing a post-apply bake (PAB) of the deposited photoresist layer to remove residual moisture from the layer to form a film; or pretreating the photoresist layer in any useful manner. The optional PAB can be performed after film deposition but before EUV exposure. The PAB can also combine thermal treatment, chemical exposure, and moisture to increase the EUV sensitivity of the film, thereby reducing the EUV dose required to develop a pattern in the film. In certain embodiments, the PAB step is performed at a temperature greater than about 100°C, or at a temperature between about 100°C and about 200°C, or between about 100°C and about 250°C. In some cases, PAB is not performed within the method.

[0087] In operation 308, the coating is exposed to EUV radiation to develop the pattern. Generally, the EUV exposure causes a change in the chemical composition of the coating, creating an etch selectivity contrast that can be used to remove portions of the coating. Such contrast can provide a positive-tone resist or a negative-tone resist as described herein. The EUV exposure can include, for example, exposure having a wavelength in a range of about 10 nm to about 20 nm in a vacuum environment (e.g., about 13.5 nm in a vacuum environment).

[0088] Operation 310 is an optional post-exposure bake (PEB) of the exposed film to further remove residual moisture, promote chemical concentration within the film, increase the etch selectivity contrast of the exposed film, or post-treat the film in any useful manner. Non-limiting examples of temperatures for PEB include, for example, about 90°C to 600°C, 100°C to 400°C, 125°C to 300°C, 170°C to 250°C or higher, 190°C to 240°C, as well as other temperatures described herein. In one example, the exposed film can be thermally treated (e.g., optionally in the presence of various chemical species) to promote reactivity within the EUV-exposed portions of the resist upon exposure to a stripper (e.g., a halide-based etchant such as HCl, HBr, H2, Cl2, Br2, BCl3, or combinations thereof, as well as any halide-based development process described herein; an aqueous alkaline developer solution; or an organic developer solution) or a positive tone developer. In another example, the exposed film can be heat treated to further crosslink the ligands in the EUV-exposed portions of the resist, thereby providing EUV-unexposed portions that can be selectively removed upon exposure to a stripper (e.g., a negative tone developer).

[0089] Then, in operation 312, the PR pattern is developed. In various embodiments of development, either the exposed areas are removed (providing a pattern in a positive resist) or the unexposed areas are removed (providing a pattern in a negative resist). In various embodiments, such a step can be a dry process or a wet process. In certain embodiments, the development step is a dry process (e.g., with a gaseous etchant such as HBr, HCl, HBr, HI, HF, Cl2, Br2, BCl3, BF3, NF3, NH3, SOCl2, SF6, CF4, CHF3, CH2F2, and / or CH3F, as well as other halides described herein, and in the optional presence of a plasma). In other embodiments, the development step is a wet process (e.g., with an organic solvent as described herein).

[0090] For pure Ta-based PR coatings, wet development can be achieved using a non-polar solvent that differentiates between the non-polar, low-molecular-weight species in the unexposed areas of the PR and the dense, high-molecular-weight species in the printed areas of the lithographically exposed material. Non-limiting solvents include, for example, alcohols (e.g., isopropyl alcohol (IPA)), ketones (e.g., 2-heptanone, cyclohexanone, or acetone), or glycol ethers (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA)), as well as others described herein, and combinations thereof. Dry development can include halide etch chemistries (e.g., Cl2, NF3, SOCl2, SF6, CF4, CHF3, CH2F2, and / or CH3F etch, or any of those described herein).

[0091] For mixed Ta- and Sn-based PR films, wet development can be accomplished using non-polar solvents (e.g., as described herein for pure Ta-based films). Dry development can include halide etch chemistries containing a mixture of halides (e.g., HBr, BCl3, Cl2, and / or NF3 etching in a single step or series of steps).

[0092] The developing step can include the use of gas phase halide chemicals (e.g., HBr chemicals) or liquid phase aqueous or organic solvents. The developing step can include any useful experimental conditions that may be combined with any useful chemicals (e.g., halide chemicals or aqueous chemicals), such as low pressure conditions (e.g., from about 1 mTorr to about 100 mTorr), plasma exposure (e.g., in the presence of a vacuum), and / or thermal conditions (e.g., at temperatures from about -10°C to about 100°C). The developing can include, for example, a halide-based etchant, such as HCl, HBr, H2, Cl2, Br2, BCl3, NF3, or combinations thereof, as well as any of the halide-based developing processes described herein; an aqueous alkaline developing solution; or an organic developing solution. In certain embodiments, development can include more aggressive conditions, such as extended development times, higher pressure conditions (e.g., about 100 mTorr to 900 mTorr), higher temperature conditions (e.g., 20°C to 120°C), stronger dry etchants (e.g., NF3), or wet developers with stronger acids or bases (e.g., phosphorous-containing inorganic acids). Additional development process conditions are described herein.

[0093] In another example, the method can include curing the patterned coating (e.g., after development) to provide a resist mask disposed on the upper surface of the substrate. The curing step can include any useful treatment for further crosslinking or reacting the EUV-unexposed or exposed regions, such as exposure to plasma (e.g., O, Ar, He, or CO plasma), exposure to ultraviolet light, annealing (e.g., at temperatures between about 180°C and about 240°C), thermal baking, or combinations thereof, which may be useful for a post-development bake (PDB) step. Additional post-application treatments are described herein and may be performed as optional steps in any of the methods described herein.

[0094] Deposition can include the use of other metal precursors. As seen in FIG. 3B, method 320 can include deposition 322 of a film from a Ta-based precursor and an Sn-based precursor, which can optionally include the presence of a counter reactant, a reducing gas, a hydrocarbon, and / or an alkyne. Such processes can include ALD or CVD, in which case mixed Ta-based and Sn-based precursors can be prepared by flowing Ta-based and Sn-based precursors with or without a reducing gas (e.g., any of those described herein) and growing to a desired film thickness. Precursor concentrations, flow rates, and / or deposition times can be varied to fine-tune the composition and properties of the mixed metal, alloy-like film. In this manner, the relative amounts of Ta-based and Sn-based precursors deposited as a film can be optimized.

[0095] The resulting coating is a mixed metal coating, which can be optionally cleaned 324 and optionally subjected to PAB or pre-treatment 326. The mixed metal coating can also be a PR coating, where EUV exposure 328 generates a PR pattern and development 332 provides a pattern in the coating. The exposed coating can optionally be subjected to PEB or post-treatment 330.

[0096] Such precursors can be provided in any useful manner. As seen in FIG. 3C , method 340 can include depositing 342 a Ta-based precursor 342A on a film, followed by or preceded by depositing 342 a Sn-based precursor 342B. The precursors can be provided sequentially in any useful manner. Some exemplary sequences can include one or more cycles, such as n cycles (e.g., n is 1 to 100) of alternating Ta-containing and Sn-containing layers. The sequence used can be determined by any of a number of factors, such as to build or even customize a film having a desired thickness, a desired average patterning radiation sensitivity, a desired profile or gradient of patterning radiation sensitivity, desired mechanical properties, or some combination thereof. As shown, operation 342A produces a Ta-containing layer, and operation 342B produces a Sn-based layer. These operations 342A, 342B can optionally be performed in the presence of a counter reactant, a reducing gas, a hydrocarbon, or an alkyne.

[0097] In addition to deposition by CVD, mixed Ta- and Sn-based PR films can be prepared by two- or more-step ALD. In one example, a two-step process may include (i) Sn-based oxide deposition with a Sn-based precursor and optional counter reactant followed by gas purging, followed by (ii) Ta-based oxide or nitride deposition with a Ta-based precursor and optional reducing gas / alkyne followed by purging, where each of (i) and (ii) can be repeated until the desired film thickness is achieved. Operations (i) and (ii) can be performed in reverse order, i.e., Ta-based precursor is deposited first, followed by Sn-based precursor. Alternatively, operations (i) and (ii) can be repeated n times by cycles of (i) (e.g., (i)1, (i)2, ...(i) n );(ii) n cycles (e.g., (ii)1, (ii)2, ...(ii) n ); (i) n cycles followed by (ii) m cycles (e.g., (i)1, (i)2, ...(ii) n, (ii)1, (ii)2, ...(ii) m , where n may or may not be equal to m); or (i) followed by n cycles of (ii) (e.g., (i) 1, (ii) 1, ... (i) n , (ii) m , where n may or may not be equal to m).

[0098] In another example, a three-step process may include (i) Sn-based oxide deposition from a Sn-based precursor and optional counter reactant followed by a gas purge; (ii) application of Ta-based oxide or nitride deposition from a Ta-based precursor and optional reducing gas / alkyne followed by a gas purge; and (iii) application of a reducing gas (e.g., any described herein) followed by a gas purge, which may be repeated until a desired coating thickness is achieved.

[0099] The resulting coating may be a layered coating, which may be optionally cleaned 344 and optionally subjected to PAB or pre-treatment 346. The layered coating may be a PR coating, where EUV exposure 348 generates a PR pattern and development 352 provides a pattern in the coating. The exposed coating may optionally be subjected to PEB or post-treatment 350.

[0100] Any useful type of chemical can be used during the deposition, patterning, and / or development steps. Such steps can be based on dry processes using gas-phase chemicals or wet processes using wet-phase chemicals. Various embodiments include combining any of the dry operations of deposition, (EUV) lithography photopatterning, dry stripping, and dry development to form a film. Various other embodiments include advantageously combining the dry processing operations described herein with wet processing operations, for example, combining a spin-on EUV photoresist (wet process), such as that available from Inpria Corp., with dry development or other wet or dry processes described herein. In various embodiments, wafer cleaning can be a wet process described herein, and the other processes are dry processes. In still other embodiments, a wet development process can be used.

[0101] Without intending to limit the mechanism, function, or utility of the present technology, the dry processing of the present technology may offer various benefits over wet processing. For example, the dry deposition techniques described herein can be used to deposit thinner and less defective films than can be applied using spin-coating techniques, and the exact thickness of the deposited film can be adjusted and controlled by simply increasing or decreasing the length of the deposition step or sequence.

[0102] In other embodiments, dry and wet operations can be combined to provide a dry / wet process. Within any of the processes described herein (e.g., lithography processes, deposition processes, EUV exposure processes, development processes, pre-processing processes, post-coating processes, etc.), various specific operations can include wet, dry, or wet and dry embodiments. For example, wet deposition can be combined with dry development; or wet deposition can be combined with wet development; or dry deposition can be combined with wet development; or dry deposition can be combined with dry development. Any of these can, in turn, be combined with the wet or dry pre- and post-coating processes described herein.

[0103] Thus, in some non-limiting embodiments, dry processing can offer more tunability and result in further critical dimension (CD) control and scum removal. Dry development can improve performance (e.g., by preventing line collapse due to surface tension in wet development) and / or enhance throughput (e.g., by avoiding wet development tracks). Other advantages may include eliminating the use of organic solvent developers, reducing susceptibility to adhesion problems, avoiding the need for wet resist formulation application and removal (e.g., avoiding scum formation and pattern distortion), improving line edge roughness, patterning directly to device topography, providing the ability to tailor hard mask chemistries to specific substrates and semiconductor device designs, and avoiding other solubility-based limitations. Additional details, materials, processes, steps, and apparatus are described herein.

[0104] Ta-based precursor Any useful Ta-based precursors and other metal compounds (e.g., organometallic compounds) can be used in the methods and processes herein. Non-limiting Ta-based precursors and organometallic compounds are described herein.

[0105] The Ta-based precursor may include any precursor (e.g., as described herein) that provides a patternable coating (or patterned radiation-sensitive coating or photopatternable coating) that is sensitive to radiation. Such radiation may include EUV or DUV radiation provided by irradiating through a patterning mask, thereby providing the patterning radiation. Exposure to such radiation can alter the coating itself, making it radiation-sensitive.

[0106] In certain embodiments, the Ta-based precursor is an organometallic compound that includes at least one Ta center and at least one ligand that can react with a reducing gas or an alkyne. In some non-limiting embodiments, the Ta-based precursor also includes organic moieties that can be reactive in the presence of patterning radiation, such as by undergoing removal or exclusion from the metal center or by reacting or polymerizing with other moieties in the film.

[0107] In some embodiments, the Ta-based precursor has the formula (I): TaR b L c (I) and During the ceremony, each R is independently an EUV labile group, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted imino, or optionally substituted alkylene; each L is independently a ligand or other moiety that is reactive with a reducing gas or an alkyne; b≧0; and c≧0. In other embodiments, b is 1 and c is 3. In other embodiments, c > 1. In still other embodiments, b > 1. In certain embodiments, L is an optionally substituted amino (e.g., -NR N1 R N1 where each R N1 and R N2 are independently H or optionally substituted alkyl, such as methyl, ethyl, butyl, isopropyl, t-butyl, n-butyl, etc. In some embodiments, R is a double bond ligand (e.g., ═NR i or =CR i R ii where each R i and R ii are EUV-labile groups including, independently, H, optionally substituted linear alkyl, optionally substituted branched alkyl, or optionally substituted cycloalkyl, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-butyl, etc.

[0108] In other embodiments, the Ta-based precursor has the formula (IA): R=Ta(L) b (IA) and During the ceremony, R = NR i or =CR i R ii and; Each L is independently halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or a divalent ligand bonded to Ta, wherein the divalent ligand is -NR i -Ak-NR ii - and; Each R i and R ii are independently H, optionally substituted linear alkyl, optionally substituted branched alkyl, or optionally substituted cycloalkyl; Ak is optionally substituted alkylene or optionally substituted alkenylene; b≧1.

[0109] In some embodiments, the optionally substituted amino is —NR 1 R 2 where each R 1 and R 2 are independently H or alkyl; or R 1 and R 2 taken together with the nitrogen atom to which each is attached form a heterocyclyl group, as defined herein. In other embodiments, an optionally substituted bis(trialkylsilyl)amino is —N(SiR 1 R 2 R 3 )2, wherein each R 1 , R 2 , and R 3are independently optionally substituted alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR 1 R 2 R 3 where each R 1 , R 2 , and R 3 is independently an optionally substituted alkyl. Any of the substituents R and L of formulas (I) and (IA) can also be used as R or L in any of formulas (II), (II-A), (III), (IV), (V), (VI), (VII), (VIII), or (IX) described herein.

[0110] In some embodiments, the Ta-based precursor is N1 R N2 )3, wherein R N1 and R N2 each independently represents an optionally substituted alkyl (e.g., methyl, ethyl, butyl, isopropyl, t-butyl, n-butyl, etc.), and R represents a double bond ligand (e.g., ═NR i or =CHR i where R i (wherein is an optionally substituted alkyl, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, or n-butyl.) In such precursors, the double-bonded ligand serves as both the nitrogen source and the EUV-labile group, while the three amino-based ligands serve as reactive sites for bonding with existing functional groups on the deposition substrate surface.

[0111] Non-limiting Ta-based precursors include pentakis(dimethylamino)tantalum(V) (Ta[NMe]), t-amylimidotris(dimethylamino)tantalum(V) (Ta(=N-CHMeEt)(NMe), (t-butylimido)tris(diethylamino)tantalum(V) (Ta(=Nt-Bu)(NEt)), (t-butylimido)tris(dimethylamino)tantalum(V) (Ta(=Nt-Bu)(NEt)), and (t-butylimido)tris(ethylmethylamino)tantalum(V) (Ta(=Nt-Bu)(NMeEt)).

[0112] Further metal precursors The methods herein can include a Ta-based precursor used in combination with any useful metal precursor. In particular examples, the metal precursor is a Sn-based precursor, an organometallic compound, or any of the additional metal precursors described below.

[0113] The metal precursor can include any precursor (e.g., as described herein) that provides a patternable coating (or patterned radiation-sensitive coating or photopatternable coating) that is sensitive to radiation. Such radiation can include EUV radiation, DUV radiation, or UV radiation, provided by irradiating through a patterning mask, thereby providing the patterning radiation. Exposure to such radiation can alter the coating itself, making it radiation-sensitive. In certain embodiments, the metal precursor is an organometallic compound that includes at least one metal center.

[0114] The metal precursor can have any useful number and type of ligands. In some embodiments, the ligands can be characterized by their ability to react in the presence of a counter reactant or in the presence of patterning radiation. For example, the metal precursor can include a ligand (e.g., a dialkylamino group or an alkoxy group) that reacts with a counter reactant, which can introduce a linkage (e.g., an -O- linkage) between the metal centers. In another example, the metal precursor can include a ligand that desorbs in the presence of patterning radiation. Such a ligand can include a branched or linear alkyl group with a beta hydrogen.

[0115] The metal precursor may be any useful metal-containing precursor, such as an organometallic compound, an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In a non-limiting example, the organometallic compound has the formula (II): M a R b L c (II) and During the ceremony, M is a metal or atom with a high EUV absorption cross section; each R is independently an EUV-labile ligand, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is independently a ligand (e.g., an anionic, neutral, or multidentate ligand), ion, or other moiety that is reactive with a counter reactant, and R and L together with M can optionally form a heterocyclyl group, or R and L together can optionally form a heterocyclyl group; a≧1; b≧1; and c≧1.

[0116] In some embodiments, R is optionally substituted alkyl and M is tin. In other embodiments, each L is independently H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy. In certain embodiments, L is optionally substituted amino (e.g., -NR 1 R 2 where each R 1 and R 2 are independently optionally substituted alkyl).

[0117] In some embodiments, the organometallic compound is SnRL, where each L is independently an optionally substituted amino (e.g., —NR 1 R 2 and each R 1 and R 2 are independently optionally substituted alkyl such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, etc.), and R is optionally substituted alkyl (e.g., methyl, ethyl, butyl, isopropyl, tert-butyl, n-butyl, etc.).

[0118] In some embodiments, each ligand in the metal precursor may be a ligand reactive with a counter reactant. In one example, the metal precursor comprises a structure having formula (II), where each R is independently L. In another example, the metal precursor comprises a structure having formula (II-A): M a L c (II-A) and During the ceremony, M is a metal or atom with a high EUV absorption cross section; each L is independently a ligand, ion, or other moiety reactive with a counter reactant, and two L together can optionally form a heterocyclyl group; a≧1; and c≧1. In certain embodiments of Formula (II-A), a is 1. In further embodiments, c is 2, 3, or 4.

[0119] In another non-limiting example, the metal precursor has the formula (IV): M a R b (III) and During the ceremony, M is a metal or atom with a high EUV absorption cross section; each R is independently H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, an anionic ligand, a neutral ligand, or a multidentate ligand; a≧1; and b≧1.

[0120] In any formula herein, M represents a high patterning radiation absorption cross section (e.g., 1×10 7 cm 2M may be a metal, metalloid, or atom having an EUV absorption cross section equal to or greater than 1 / mol. In some embodiments, M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), tantalum (Ta), cesium (Cs), indium (In), molybdenum (Mo), hafnium (Hf), iodine (I), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), platinum (Pt), and lead (Pb). In further embodiments, in Formula (II), (II-A), or (III), M is Sn, a is 1, and c is 4. In other embodiments, in Formula (II), (II-A), or (III), M is Sn, a is 1, and c is 1 or 2. In certain embodiments, M is Sn(II) (e.g., in formula (II), (II-A), or (III)), thereby providing a metal precursor that is a Sn(II)-based compound. In other embodiments, M is Sn(IV) (e.g., in formula (II), (II-A), or (III)), thereby providing a metal precursor that is a Sn(IV)-based compound. In certain embodiments, the precursor comprises iodine (e.g., in periodate).

[0121] In any formula herein, each R or L is independently H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy (e.g., -OR 1 where R 1 may be optionally substituted alkyl), optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, anionic ligands (e.g., oxide, chloride, hydride, acetate, iminodiacetate, etc.), neutral ligands, or polydentate ligands.

[0122] In some embodiments, the optionally substituted amino is —NR 1 R 2 where each R 1 and R 2 are independently H or alkyl; or R 1 and R 2 taken together with the nitrogen atom to which each is attached form a heterocyclyl group, as defined herein. In other embodiments, an optionally substituted bis(trialkylsilyl)amino is —N(SiR 1 R 2 R 3 )2, wherein each R 1 , R 2 , and R 3 are independently optionally substituted alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR 1 R 2 R 3 where each R 1 , R 2 , and R 3 is independently an optionally substituted alkyl.

[0123] In other embodiments, the formula is —NR 1 R 2 The first R (or the first L) and -NR 1 R 2 where each R 1 and R 2 are independently H or optionally substituted alkyl; or R of the first R (or the first L) 1 and the R of the second R (or second L) 1 taken together with the nitrogen atom and metal atom to which each is attached to form a heterocyclyl group, as defined herein. In yet other embodiments, the formula is -OR 1 The first R and -OR 1 where each R 1 are independently H or optionally substituted alkyl; or R of the first R 1 and the second R1 taken together with the oxygen atom and metal atom to which each is attached form a heterocyclyl group as defined herein.

[0124] In some embodiments, at least one of R or L (e.g., in Formula (II), (II-A), or (III)) is an optionally substituted alkyl. Non-limiting alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl, C n H 2n+1 where n is 1, 2, 3, or greater. In various embodiments, R or L has at least one beta hydrogen or beta fluorine.

[0125] In some embodiments, each R or L or at least one R or L (e.g., in Formula (II), (II-A), or (III)) is halo. In particular, the metal precursor may be a metal halide. Non-limiting metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0126] In some embodiments, each R or L, or at least one R or L (e.g., in Formula (II), (II-A), or (III)) may contain a nitrogen atom. In certain embodiments, one or more R or L may be an optionally substituted amino, an optionally substituted monoalkylamino (e.g., —NR 1 H, where R 1 is optionally substituted alkyl), optionally substituted dialkylamino (e.g., —NR 1 R 2 where each R 1 and R 2are independently optionally substituted alkyl), or optionally substituted bis(trialkylsilyl)amino. Non-limiting examples of R and L substituents include -NMe, -NHMe, -NEt, -NHEt, -NMeEt, -N(t-Bu)-[CHCH]-N(t-Bu)-(tbba), -N(SiMe), and -N(SiEt).

[0127] In some embodiments, each R or L, or at least one R or L (e.g., in Formula (II), (II-A), or (III)) may contain a silicon atom. In certain embodiments, one or more R or L may be an optionally substituted trialkylsilyl or an optionally substituted bis(trialkylsilyl)amino. Non-limiting R or L substituents may include, for example, -SiMe, -SiEt, -N(SiMe), and -N(SiEt).

[0128] In some embodiments, each R or L, or at least one R or L (e.g., in Formula (II), (II-A), or (III)) may contain an oxygen atom. In certain embodiments, one or more R or L may be optionally substituted alkoxy or optionally substituted alkanoyloxy. Non-limiting R or L substituents include, for example, methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), acetate (-OC(O)-CH), and -O=C(CH)-CH=C(CH)-O-(acac).

[0129] Any formula herein may include one or more neutral ligands. Non-limiting neutral ligands include optionally substituted amine, optionally substituted ether, optionally substituted alkyl, optionally substituted alkene, optionally substituted alkyne, optionally substituted benzene, oxo, or carbon monoxide.

[0130] Any formula herein may include one or more polydentate (e.g., bidentate) ligands. Non-limiting polydentate ligands include diketonates (e.g., acetylacetonate (acac) or -OC(R 1 )-Ak-(R 1 )CO- or -OC(R 1 )-C(R 2 )-(R 1 )CO-), bidentate chelate dinitrogen (e.g., -N(R 1 )-Ak-N(R 1 )- or -N(R 3 )-CR 4 -CR 2 =N(R 1 )-), aromatic (e.g., -Ar-), amidinates (e.g., -N(R 1 )-C(R 2 )-N(R 1 )-), aminoalkoxides (e.g., -N(R 1 )-Ak-O- or -N(R 1 )2-Ak-O-), diazadienyl (e.g., -N(R 1 )-C(R 2 )-C(R 2 )-N(R 1 )-), cyclopentadienyl, pyrazolate, optionally substituted heterocyclyl, optionally substituted alkylene, or optionally substituted heteroalkylene. In certain embodiments, each R 1 are independently H, optionally substituted alkyl, optionally substituted haloalkyl, or optionally substituted aryl; each R 2 are independently H or optionally substituted alkyl; R 3 and R 4 are taken together to form an optionally substituted heterocyclyl; Ak is an optionally substituted alkylene; and Ar is an optionally substituted arylene.

[0131] In certain embodiments, the metal precursor comprises tin. In some embodiments, the tin precursor comprises SnR or SnR2 or SnR4 or R3SnSnR3, where each R is independently H, halo, optionally substituted C 1~12 Alkyl, optionally substituted C 1~12 alkoxy, optionally substituted amino (e.g., —NR 1 R 2 ), optionally substituted C 2~12 Alkenyl, optionally substituted C 2~12 Alkynyl, optionally substituted C 3~8 Cycloalkyl, optionally substituted aryl, cyclopentadienyl, optionally substituted bis(trialkylsilyl)amino (e.g., —N(SiR 1 R 2 R 3 )2), optionally substituted alkanoyloxy (e.g., acetate), diketonate (e.g., —OC(R 1 )-Ak-(R 2 )CO-), or bidentate chelate dinitrogen (e.g., -N(R 1 )-Ak-N(R 1 In certain embodiments, each R 1 , R 2 , and R 3 are independently H or C 1~12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl); Ak is optionally substituted C 1~6Non-limiting examples of tin precursors include SnF, SnH, SnBr, SnCl, SnI, tetramethyltin (SnMe), tetraethyltin (SnEt), trimethyltin chloride (SnMeCl), dimethyltin dichloride (SnMeCl), methyltin trichloride (SnMeCl), tetraallyltin, tetravinyltin, hexaphenylditin(IV) (PhSn-SnPh), where Ph is fluorine. phenyl), dibutyldiphenyltin (SnBu2Ph2), trimethyl(phenyl)tin (SnMe3Ph), trimethyl(phenylethynyl)tin, tricyclohexyltin hydride, tributyltin hydride (SnBu3H), dibutyltin diacetate (SnBu2(CH3COO)2), tin(II) acetylacetonate (Sn(acac)2), SnBu3(OEt), SnBu2(OMe)2, SnBu3(OMe), S n(t-BuO)4, Sn(n-Bu)(t-BuO)3, tetrakis(dimethylamino)tin (Sn(NMe2)4), tetrakis(ethylmethylamino)tin (Sn(NMeEt)4), tetrakis(diethylamino)tin(IV) (Sn(NEt2)4), (dimethylamino)trimethyltin(IV) (Sn(Me)3(NMe2), Sn(i-Pr)(NMe2)3, Sn(n-Bu)(NMe2)3, Sn(s-Bu) (NMe2)3, Sn(i-Bu)(NMe2)3, Sn(t-Bu)(NMe2)3, Sn(t-Bu)2(NMe2)2, Sn(t-Bu)(NEt2)3, Sn(tbba), Sn(II) (1,3-bis(1,1-dimethylethyl)-4,5-dimethyl-(4R,5R)-1,3,2-diazastannolidin-2-ylidene), or bis[bis(trimethylsilyl)amino]tin ((SiMe3)2]2).

[0132] In other embodiments, the metal precursor comprises bismuth, such as BiR3, where each R is independently halo, optionally substituted C 1~12 Alkyl, mono-C 1~12 Alkylamino (e.g., -NR 1 H), Di-C 1~12 Alkylamino (e.g., -NR 1 R 2), optionally substituted aryl, optionally substituted bis(trialkylsilyl)amino (e.g., —N(SiR 1 R 2 R 3 )2), or diketonates (e.g., -OC(R 4 )-Ak-(R 5 )CO-). In certain embodiments, each R 1 , R 2 , and R 3 independently, C 1~12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl); 4 and R 5 are independently H or optionally substituted C 1~12 and alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl). Non-limiting bismuth precursors include BiCl, BiMe, BiPh, Bi(NMe), Bi[N(SiMe)], and Bi(thd), where thd is 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0133] In other embodiments, the metal precursor comprises tellurium, such as TeR2 or TeR4, where each R is independently halo, optionally substituted C 1~12 Alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), optionally substituted C 1~12 alkoxy, optionally substituted aryl, hydroxyl, oxo, or optionally substituted trialkylsilyl. Non-limiting tellurium precursors include dimethyltellurium (TeMe), diethyltellurium (TeEt), di(n-butyl)tellurium (Te(n-Bu)), di(isopropyl)tellurium (Te(i-Pr), di(t-butyl)tellurium ((t-Bu)), hydride t-butyltellurium (Te(t-Bu)(H)), Te(OEt), bis(trimethylsilyl)tellurium (Te(SiMe)), and bis(triethylsilyl)tellurium (Te(SiEt)).

[0134] The metal precursor may also include cesium. Non-limiting cesium precursors include Cs(OR), where R is an optionally substituted C 1~12 It is alkyl or optionally substituted aryl. Other cesium precursors include Cs(Ot-Bu) and Cs(Oi-Pr).

[0135] The metal precursor may include antimony, such as SbR3, where each R is independently halo, optionally substituted C 1~12 Alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), optionally substituted C 1~12 alkoxy, or optionally substituted amino (e.g., —NR 1 R 2 where each R 1 and R 2 are independently H or optionally substituted C 1~12 Non-limiting antimony precursors include SbCl, Sb(OEt), Sb(On-Bu), and Sb(NMe).

[0136] Other metal precursors include indium precursors such as InR3, where each R is independently halo, optionally substituted C 1~12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), or diketonate (e.g., -OC(R 4 )-Ak-(R 5 )CO-, where each R 4 and R 5 are independently H or C 1~12 Non-limiting indium precursors include InCp, where Cp is cyclopentadienyl, InCl, InMe, In(acac), In(CFCOCHCOCH), and In(thd).

[0137] Still other metal precursors include molybdenum precursors such as MoR4, MoR5, or MoR6, where each R is independently an optionally substituted C 1~12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), optionally substituted aryl (e.g., allyl such as C3H5 or an oxide of allyl such as C5H5O), optionally substituted alkylimido (e.g., =NR 1 ), acetonitrile, optionally substituted amino (e.g., —NR 1 R 2 ), halo (e.g., chloro or bromo), carbonyl, diketonate (e.g., -OC(R 3 )-Ak-(R 3 )CO-), or bidentate chelate dinitrogen (e.g., -N(R 3 )-Ak-N(R 3 )- or -N(R 4 )-CR 5 -CR 2 =N(R 3 In certain embodiments, each R 1 and each R 2 are independently H or optionally substituted alkyl; each R 3 are independently H, optionally substituted alkyl, optionally substituted haloalkyl, or optionally substituted aryl; R 4 and R 5 taken together form an optionally substituted heterocyclyl. Non-limiting molybdenum precursors include Mo(CO), bis(t-butylimido)bis(dimethylamino)molybdenum(VI) or Mo(NMe)(=Nt-Bu), molybdenum(VI) dioxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate) or Mo(=O)(thd), or Mo(η 3 and molybdenum allyl complexes such as molybdenum-allyl)X(CO)2(CH3CN)2, where allyl is C3H5 or C5H5O and X can be Cl, Br, or alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl).

[0138] Metal precursors can also include hafnium precursors such as HfR3 or HfR4, where each R is independently an optionally substituted C 1~12 Alkyl, optionally substituted C 1~12 Alkoxy, Mono-C 1~12 Alkylamino (e.g., -NR 1 H, where R 1 is optionally substituted C 1~12 alkyl), di-C 1~12 Alkylamino (e.g., -NR 1 R 2 where each R 1 and R 2 are independently optionally substituted C 1~12 alkyl), optionally substituted aryl (e.g., phenyl, benzene, or cyclopentadienyl, as well as substituted forms thereof), optionally substituted aryl (e.g., allyl or allyl oxide), or diketonate (e.g., —OC(R 4 )-Ak-(R 5 )CO-, where each R 4 and R 5 are independently H or optionally substituted C 1~12 Non-limiting hafnium precursors include Hf(i-Pr)(NMe2)3; Hf(η-C6H5R 1 )(η-C3H5)2(wherein, R 1 is H or alkyl); HfR 1 (NR 2 R 3 )3(wherein, R 1 , R 2 , and R 3 each independently optionally substituted C 1~12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl); HfCp2Me2; Hf(Ot-Bu)4; Hf(OEt)4; Hf(NEt2)4; Hf(NMe2)4; Hf(NMeEt)4; and Hf(thd)4.

[0139] Further metal precursors and non-limiting substituents are described herein. For example, the metal precursor may be any of the metal precursors having the structure of formula (II), (II-A), or (III) described above, or formula (IV), (V), (VI), (VII), (VIII), or (IX) described below. Any of the substituents M, R, X, or L described herein can be used in any of formulas (II), (II-A), (III), (IV), (V), (VI), (VII), (VIII), or (IX).

[0140] Various atoms present in the Ta-based precursor, metal precursor, reducing gas, hydrocarbon, alkyne, and / or counter reactant can be provided in a gradient film. In some embodiments of the techniques discussed herein, a non-limiting strategy that can further improve the EUV sensitivity of a photoresist (PR) film is to create a film in which the film composition is vertically graded, resulting in depth-dependent EUV sensitivity. Homogeneous PR with a high absorption coefficient requires a higher EUV dose to ensure that the bottom is fully exposed because the light intensity decreases with depth in the film. Increasing the density of atoms with high EUV absorption at the bottom of the film compared to the top of the film (i.e., creating a gradient of increasing EUV absorption) allows for more efficient use of available EUV photons while making the absorption distribution (and secondary electron effects) more uniform toward the bottom of the film, which is more highly absorbing. In one non-limiting example, the gradient film includes Te, I, or other atoms toward the bottom of the film (e.g., closer to the substrate).

[0141] The strategy of designing vertical compositional gradients in PR films is particularly applicable to dry deposition methods such as MLD, CVD, and ALD, and can be achieved by adjusting the flow ratio between different reactants during deposition. The types of compositional gradients that can be designed include ratios between different highly absorbing metals, percentages of metal atoms with EUV-cleavable organic groups, Ta-based precursors, Sn-based precursors, percentages of other metal precursors, and / or counter reactants containing highly absorbing elements, as well as combinations of the above.

[0142] Compositional gradients in EUV PR films also offer additional benefits. For example, a high density of highly EUV-absorbing elements at the bottom of the film effectively generates more secondary electrons that can better expose the upper portion of the film. Additionally, such compositional gradients may directly correlate with a higher proportion of EUV-absorbing species that are not attached to bulky terminal substituents. For example, in the case of Sn-based resists, it is possible to incorporate tin precursors with four leaving groups, which promotes the formation of Sn-O-substrate bonds at the interface and improves adhesion.

[0143] Such gradient coatings can be formed by using any of the metal precursors (e.g., Ta-based, Sn-based, or other metal-based precursors) and / or counter reactants described herein. Still other coatings, methods, precursors, and other compounds are described in U.S. Provisional Patent Application No. 62 / 909,430, filed October 2, 2019, and International Application No. PCT / US20 / 53856, filed October 1, 2020, published as WO 2021 / 067632 (each of which is entitled SUBSTRATE SURFACE MODIFICATION WITH HIGH EUV ABSORBERS FOR HIGH PERFORMANCE EUV PHOTORESISTS); and PHOTORESIST WITH MULTIPLE PATTERNING RADIATION-ABSORBING ELEMENTS AND / OR VERTICAL COMPOSITION, filed June 24, 2020. No. PCT / US20 / 70172, entitled "GRADIENT," the disclosure of which is incorporated herein by reference, at least with respect to the composition, deposition, and patterning of directly photopatternable metal oxide films to form EUV resist masks.

[0144] Furthermore, two or more different precursors can be used within each layer (e.g., coating). For example, two or more of any metal-containing precursors herein can be used to form an alloy. In one non-limiting example, a tin precursor containing an -NR2 ligand can be used with an RTiH, RTiD, or TeR2 precursor (where R is alkyl, particularly t-butyl or i-propyl) to form tin telluride. In another example, a first metal precursor containing an alkoxy or halo ligand (e.g., SbCl3) can be used with a tellurium-containing precursor containing a trialkylsilyl ligand (e.g., bis(trimethylsilyl)tellurium) to form a metal telluride.

[0145] Still other exemplary EUV-sensitive materials, as well as processing methods and apparatus, are described in U.S. Pat. No. 9,996,004 and WO 2019 / 217749, each of which is incorporated herein by reference in its entirety.

[0146] As described herein, the coatings, layers, and methods herein can be used with any useful precursor. In some cases, the metal precursor has the following formula (IV): MX n (IV) and a metal halide having the formula: where M is a metal, X is halo, and n is 2-4, depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0147] Another non-limiting metal-containing precursor has the formula (V): MR n (V) and wherein M is a metal; each R is independently H, optionally substituted alkyl, amino (e.g., -NR2 where each R is independently alkyl), optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR3)2 where each R is independently alkyl), or optionally substituted trialkylsilyl (e.g., -SiR3 where each R is independently alkyl); and n is 2 to 4, depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. The alkyl group can be C n H 2n+1 where n is 1, 2, 3, or greater. Exemplary organometallic agents include SnMe4, SnEt4, TeR n, RTeR, t-butyl tellurium hydride (Te(t-Bu)(H)), dimethyl tellurium (TeMe2), di(t-butyl) tellurium (Te(t-Bu)2), di(isopropyl) tellurium (Te(i-Pr)2), bis(trimethylsilyl) tellurium (Te(SiMe3)2), bis(triethylsilyl) tellurium (Te(SiEt3)2), tris(bis(trimethylsilyl)amido)bismuth (Bi[N(SiMe3)2]3), and Sb(NMe2)3.

[0148] Another non-limiting metal-containing precursor is represented by the following formula (VI): ML n (VI) and a capping agent having the formula: wherein M is a metal; and each L is independently an optionally substituted alkyl, amino (e.g., —NR 1 R 2 where R 1 and R 2 each of which may be H, or alkyl such as any described herein), alkoxy (e.g., -OR, where R is alkyl such as any described herein), halo, or other organic substituent; and n is 2 to 4, depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary ligands include dialkylamino (e.g., dimethylamino, methylethylamino, and diethylamino), alkoxy (e.g., t-butoxy and isopropoxy), halo (e.g., F, Cl, Br, and I), or other organic substituent (e.g., acetylacetone or N 2 ,N 3 -di-tertbutyl-butane-2,3-diamino). Non-limiting capping agents include SnCl; SnI; Sn(NR) (where each R is independently methyl or ethyl); or Sn(t-BuO). In some embodiments, multiple types of ligands are present.

[0149] The metal-containing precursor has the following formula (VII): Rn MX m (VII) and a hydrocarbyl-substituted capping agent having the formula: where M is a metal and R is C 2~10 R is an alkyl or substituted alkyl having a beta hydrogen, and X is a suitable leaving group for reacting with the hydroxyl group of the exposed hydroxyl group. In various embodiments, n=1-3 and m=4-n, 3-n, or 2-n, with m>0 (or m≧1). For example, R can be t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n-pentyl, n-hexyl, or a derivative thereof having a heteroatom substituent at the beta position. Suitable heteroatoms include halogen (F, Cl, Br, or I) or oxygen (—OH or —OR). X can be dialkylamino (e.g., dimethylamino, methylethylamino, or diethylamino), alkoxy (e.g., t-butoxy, isopropoxy), halo (e.g., F, Cl, Br, or I), or another organic ligand. Examples of hydrocarbyl-substituted capping agents include t-butyltris(dimethylamino)tin (Sn(t-Bu)(NMe2)3), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe2)3), t-butyltris(diethylamino)tin (Sn(t-Bu)(NEt2)3), di(t-butyl)di(dimethylamino)tin (Sn(t-Bu)2(NMe2)2), sec-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe2)3), n-pentyltris(dimethylamino)tin (Sn(s-Bu)(NMe2)3), Examples of suitable tin ions include i-butyltris(dimethylamino)tin (Sn(n-pentyl)(NMe2)3), i-butyltris(dimethylamino)tin (Sn(i-Bu)(NMe2)3), i-propyltris(dimethylamino)tin (Sn(i-Pr)(NMe2)3), t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO)3), n-butyl(tris(t-butoxy)tin (Sn(n-Bu)(t-BuO)3), or isopropyltris(t-butoxy)tin (Sn(i-Pr)(t-BuO)3).

[0150] In various embodiments, the metal-containing precursor comprises at least one alkyl group on each metal atom that can survive the gas phase reaction, and other ligands or ions coordinated to the metal atom may be replaced by counter reactants. Thus, another non-limiting metal-containing precursor has the formula (VIII): M a R b L c (VIII) and an organometallic agent having the formula: wherein M is a metal; R is an optionally substituted alkyl; L is a ligand, ion, or other moiety reactive with a counter reactant; a≧1; b≧1; and c≧1. In certain embodiments, a=1 and b+c=4. In some embodiments, M is Sn, Te, Bi, or Sb. In certain embodiments, each L is independently an amino (e.g., —NR 1 R 2 where R 1 and R 2 wherein each may be H or alkyl such as any described herein), alkoxy (e.g., —OR, where R is alkyl such as any described herein), or halo (e.g., F, Cl, Br, or I). Exemplary agents include SnMeCl, SnMeCl, SnMeCl, SnMe(NMe), SnMe(NMe), and SnMe(NMe).

[0151] In other embodiments, non-limiting metal-containing precursors have the formula (IX): M a L c (IX) and an organometallic agent having the formula: wherein M is a metal; L is a ligand, ion, or other moiety that is reactive with a counter reactant; a≧1; and c≧1. In certain embodiments, c=n−1, and n is 2, 3, or 4. In some embodiments, M is Sn, Te, Bi, or Sb. The counter reactant preferably has the ability to displace the reactive moiety, a ligand or ion (e.g., L in the formulas herein), so as to link at least two metal atoms via chemical bonds.

[0152] In any embodiment herein, R is an optionally substituted alkyl (e.g., C 1~10 In one embodiment, the alkyl may be substituted with one or more halo (e.g., halo-substituted C 1 , including 1, 2, 3, 4, or more halo, such as F, Cl, Br, or I). 1~10 Exemplary R substituents include C n H 2n+1 (wherein n is preferably ≥ 3); C n F x H (2n+1-x) (In the formula, 1 ≦x≦ 2n+1 In various embodiments, R has at least one beta hydrogen or beta fluorine. For example, R may be selected from the group consisting of i-propyl, n-propyl, t-butyl, i-butyl, n-butyl, sec-butyl, n-pentyl, i-pentyl, t-pentyl, sec-pentyl, and mixtures thereof.

[0153] In any embodiment herein, L is an amino (e.g., —NR 1 R 2 where R 1 and R 2may be any moiety that is readily displaced by a counter reactant to produce an M-OH moiety, such as a moiety selected from the group consisting of: H or alkyl such as any described herein), alkoxy (e.g., —OR, where R is alkyl such as any described herein), carboxylate, halo (e.g., F, Cl, Br, or I), and mixtures thereof.

[0154] Exemplary organometallic agents include SnMeCl, (N 2 ,N 3 -di-t-butyl-butane-2,3-diamido)tin(II) (Sn(tbba)), bis(bis(trimethylsilyl)amido)tin(II), tetrakis(dimethylamino)tin(IV) (Sn(NMe2)4), t-butyltris(dimethylamino)tin (Sn(t-butyl)(NMe2)3), i-butyltris(dimethylamino)tin (Sn(i-Bu))(NMe2)3), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe2)3), se Examples include similar alkyl(tris)(t-butoxy)tin compounds such as c-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe2)3), i-propyl(tris)dimethylaminotin (Sn(i-Pr)(NMe2)3), n-propyltris(diethylamino)tin (Sn(n-Pr)(NEt2)3), and t-butyltris(t-butoxy)tin (Sn((t-BuO)3). In some embodiments, the organometallic agent is partially fluorinated.

[0155] Lithography Processing EUV lithography uses an EUV resist, which may be a polymer-based chemically amplified resist produced by a liquid-based spin-on technique or a metal oxide-based resist produced by a dry deposition technique. Such an EUV resist may include any EUV-sensitive coating or material described herein. The lithography method may include patterning the resist, for example, by exposing the EUV resist to EUV radiation to form a light pattern, and subsequently developing the pattern by removing portions of the resist according to the light pattern to form a mask.

[0156] While the present disclosure relates to lithographic patterning techniques and materials exemplified by EUV lithography, it should be understood that the present disclosure is also applicable to other next-generation lithography techniques. In addition to EUV, including the standard 13.5 nm EUV wavelength currently in use and under development, the most relevant radiation sources for such lithography are DUV (deep UV), generally referring to the use of 248 nm or 193 nm excimer laser sources; X-ray, formerly known as the X-ray range, including EUV at lower energy ranges; and electron beam, which can cover a wide energy range. Such methods include contacting a substrate (e.g., optionally having exposed hydroxyl groups) with a metal-containing precursor (e.g., any of those described herein) to form a metal oxide (e.g., a layer comprising a network of metal oxide bonds, which may also include other non-metallic and non-oxygen groups) coating as an imaging / PR layer on the surface of the substrate. The particular method may depend on the specific materials and applications used for the semiconductor substrate and the final semiconductor device. Accordingly, the methods described herein are merely exemplary of methods and materials that may be used in the present technology.

[0157] Directly photopatternable EUV resists may be composed of or include metals and / or metal oxides mixed within an organic component. Metals / metal oxides hold great promise in that they may enhance EUV photon absorption, generate secondary electrons, and / or exhibit increased etch selectivity relative to underlying film stacks and device layers. Note that both dry and wet (solvent) approaches are encompassed by the present disclosure. In wet development, the wafer may be exposed to a developing solvent, dried, and baked.

[0158] Film deposition processes including dry deposition As discussed above, the present disclosure provides methods for fabricating an imaging layer on a semiconductor substrate, where the imaging layer may be patterned using EUV or other next-generation lithography techniques. The methods include generating a vapor of a polymerized organometallic material and depositing it on a substrate. In some embodiments, any useful metal-containing precursor (e.g., a Ta-based precursor, a metal precursor, an organometallic compound, a metal halide, a capping agent, or an organometallic agent described herein) can be used for dry deposition. In other embodiments, a spin-on formulation can be used. The deposition process may include applying an EUV-sensitive material as a resist film. Exemplary EUV-sensitive materials are described herein.

[0159] The present technology includes methods by which EUV-sensitive coatings are deposited on substrates, such coatings being capable of acting as resists for subsequent EUV lithography and processing.

[0160] Such EUV-sensitive coatings include materials that, upon exposure to EUV, undergo changes such as loss of bulky pendant ligands bonded to metal atoms in low-density M-OH-rich materials, allowing crosslinking to higher-density MOM-bonded metal oxide materials. In other embodiments, EUV exposure results in further crosslinking between ligands bonded to metal atoms, thereby providing higher-density MLM-bonded organometallic materials (where L is a ligand). In yet other embodiments, EUV exposure results in loss of ligands, providing M-OH materials that can be removed with a positive tone developer.

[0161] EUV patterning creates regions of the coating with altered physical or chemical properties compared to unexposed regions. These properties can be exploited in subsequent processing, such as dissolving either the unexposed or exposed regions, or selectively depositing material onto either the exposed or unexposed regions. In some embodiments, under the conditions under which such subsequent processing is carried out, the unexposed coating has a hydrophobic surface and the exposed coating has a hydrophilic surface (it is recognized that the hydrophilic properties of the exposed and unexposed regions are relative to one another). For example, material removal may be achieved by exploiting differences in the chemical composition, density, and crosslinking of the coating. Removal may be by wet or dry processing, as further described herein.

[0162] The thickness of the EUV-patternable coating formed on the surface of a substrate may vary depending on the surface characteristics, materials used, and processing conditions. In various embodiments, the coating thickness may range from about 0.5 nm to about 100 nm. Preferably, the coating has a thickness sufficient to absorb a majority of the EUV light under EUV patterning conditions. For example, the overall absorption of the resist coating may be 30% or less (e.g., 10% or less, or 5% or less) so that the resist material at the bottom of the resist coating is fully exposed. In some embodiments, the coating thickness is 10 nm to 20 nm. While not limiting the mechanism, function, or utility of the present disclosure, it is believed that dry processes, unlike wet spin-coating processes, have fewer limitations on the surface adhesion properties of the substrate and therefore can be applied to a wider variety of substrates. Furthermore, as discussed above, the deposited coating may closely conform to surface features, providing the advantage of forming a mask on a substrate, such as a substrate with underlying features, without "filling" or otherwise planarizing such features.

[0163] The coating (e.g., imaging layer) may be comprised of a metal oxide layer deposited in any useful manner. Such a metal oxide layer can be deposited or applied by using any of the EUV-sensitive materials described herein, such as a metal-containing precursor (e.g., a metal halide, a capping agent, or an organometallic agent). In an exemplary process, a polymerized organometallic material is formed in the vapor phase or in situ on the surface of a substrate to provide a metal oxide layer. The metal oxide layer may be used as a coating, an adhesion layer, or a capping layer.

[0164] Optionally, the metal oxide layer may comprise a hydroxyl-terminated metal oxide layer that can be deposited using a capping agent (e.g., any described herein) with an oxygen-containing pair reactant. Such a hydroxyl-terminated metal oxide layer can be used as an adhesion layer between two other layers, such as, for example, between a substrate and a coating and / or between a photoresist layer and an underlayer.

[0165] Exemplary deposition techniques (e.g., for coatings) include any of those described herein, such as ALD (e.g., thermal ALD and plasma-enhanced ALD), spin-coat deposition, PVD including PVD co-sputtering, CVD (e.g., PE-CVD or LP-CVD), sputter deposition, e-beam deposition including e-beam co-evaporation, or the like, or combinations thereof, such as ALD with a CVD component, e.g., a discontinuous ALD-like process in which a metal-containing precursor and a counter reactant are separated either in time or space.

[0166] Further description of precursors applicable to the present disclosure and methods for depositing them as EUV photoresist films may be found in International Application No. PCT / US19 / 31618, entitled "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS," filed May 9, 2019, and published as WO 2019 / 217749. In addition to the Ta-based precursor, additional metal precursor, and counter reactant, the thin film may include optional materials to modify the chemical or physical properties of the film, for example, to modify the film's sensitivity to EUV or to enhance etch resistance. Such optional materials may be introduced, such as by doping during vapor formation, before deposition on the substrate, after deposition of the film, or both. In some embodiments, a mild remote H plasma may be introduced to replace some Sn-L bonds with Sn-H, thereby increasing the reactivity of the resist under EUV, for example.

[0167] In general, the method may include mixing a vapor flow of a metal precursor (e.g., a metal-containing precursor such as a Ta-based precursor, a Sn-based precursor, an organometallic compound, or an organometallic agent) with a vapor flow of an optional counter reactant to form a polymerized organometallic material, and depositing the organometallic material on a surface of a semiconductor substrate. In some embodiments, the polymerized organometallic material can be formed by mixing the metal-containing precursor with the optional counter reactant. As will be appreciated by those skilled in the art, the mixing and deposition aspects of the process may be simultaneous in a substantially continuous process.

[0168] In an exemplary sequential CVD process, two or more gas streams of a metal precursor and an optional counter reactant source are introduced into a deposition chamber of a CVD apparatus via separate inlet paths, where they mix and react in the gas phase to form an aggregate polymeric material (e.g., via metal-oxygen-metal bond formation) or a coating on a substrate. The gas streams may be introduced using, for example, separate injection inlets or a dual-plenum showerhead. The apparatus is configured so that the metal precursor and optional counter reactant flows are mixed within the chamber, allowing the metal precursor and optional counter reactant to react to form a polymerized organometallic material or a coating (e.g., a metal oxide coating material or an aggregate polymeric material, such as via metal-oxygen-metal bond formation).

[0169] When depositing metal oxide films, CVD processes are typically performed under reduced pressure, such as 0.1 Torr to 10 Torr. In some embodiments, the process is performed at a pressure of 1 Torr to 2 Torr. The temperature of the substrate is preferably below the temperature of the reactant stream. For example, the substrate temperature may be between 0°C and 250°C, or between ambient temperature (e.g., 23°C) and 150°C.

[0170] When depositing coagulated polymeric materials, CVD processes are typically performed under reduced pressure, such as 10 mTorr to 10 Torr. In some embodiments, processes are performed at 0.5 to 2 Torr. The temperature of the substrate is preferably at or below the temperature of the reactant stream. For example, the substrate temperature may be between 0°C and 250°C, or between ambient temperature (e.g., 23°C) and 150°C. In various processes, deposition of polymerized organometallic materials onto a substrate occurs at a rate inversely proportional to the surface temperature. Without intending to limit the mechanism, function, or utility of the present technology, it is believed that because the metal atoms are cross-linked reactants, the products of such gas-phase reactions have a higher molecular weight and then condense or otherwise deposit onto the substrate.

[0171] A potential advantage of using dry deposition methods is that the composition of the film can be easily adjusted as the film grows. In CVD processes, this may be achieved by varying the relative flows of the metal precursor and counter reactant during deposition. Deposition may occur at temperatures between 30°C and 200°C at pressures between 0.01 Torr and 100 Torr, more commonly between about 0.1 Torr and 10 Torr.

[0172] Films (e.g., metal oxide coating materials or aggregated polymeric materials, such as those formed by metal-oxygen-metal bond formation) may also be deposited by ALD processes. For example, a metal precursor and an optional counter reactant are introduced at separate times. This is an ALD cycle. The metal precursor reacts with the surface, forming up to a monolayer of material at a time in each cycle. This may allow for better control over the uniformity of film thickness across the surface. ALD processes are typically performed under reduced pressure, such as 0.1 Torr to 10 Torr. In some embodiments, the process is performed at 1 Torr to 2 Torr. The substrate temperature may be between 0°C and 250°C, or between ambient temperature (e.g., 23°C) and 150°C. The process may be a thermal process or, preferably, a plasma-assisted deposition.

[0173] Any of the deposition methods herein can be modified to allow for the use of two or more different metal precursors. In one embodiment, the precursors can contain the same metal but different ligands. In another embodiment, the precursors can contain different metal groups. In one non-limiting example, alternating flow of various volatile metal-containing precursors, such as using a Ta-based precursor with a Sn-based precursor, can provide a mixed metal layer. Additionally, any of the deposition methods herein can be modified to allow for the use of two or more different counter reactants.

[0174] Additionally, any of the deposition methods herein can be modified to provide one or more layers within the coating. In one example, different metal precursors can be used for each layer. In another example, the same precursors can be used for each layer, but the top layer can have a different chemical composition (e.g., different densities of metal-ligand bonds, different metals, or different binding ligands provided by adjusting or modifying the metal precursors).

[0175] The processes herein can be used to achieve surface modification. In some iterations, vapor of a metal precursor may be passed over the wafer. The wafer may be heated to provide thermal energy for the reaction to proceed. In some iterations, heating may be from about 50°C to about 250°C. In some cases, pulses of counter reactant separated by pumping and / or purging steps may be used. For example, the counter reactant may be pulsed between precursor pulses to provide ALD or ALD-like growth. In other cases, both the precursor and counter reactant may flow simultaneously. Examples of elements useful for surface modification include I, F, Sn, Bi, Sb, Te, and oxides or alloys of these compounds.

[0176] The processes herein can be used to deposit thin metal oxide or metal films by ALD or CVD. Examples include SnOx, BiOx, and Te. Following deposition, the films can be coated with M aR b L c The surface may be capped with an alkyl-substituted precursor in the form of . A counter reactant may be used to better remove the ligands, and multiple cycles may be repeated to ensure complete saturation of the substrate surface. The surface may then be ready for deposition of an EUV-sensitive coating. One possible method is to produce a thin coating of SnOx. Possible chemical reactions include the growth of SnO2 by cycling tetrakis(dimethylamino)tin with a counter reactant such as water or O2 plasma. After growth, a capping agent can be used. For example, isopropyltris(dimethylamino)tin vapor may be flowed over the surface.

[0177] The deposition process can be used on any useful surface. As referred to herein, a "surface" is a surface on which the coating of the present technology will be deposited or which will be exposed to EUV during the process. Such a surface may be on a substrate (e.g., on which the coating will be deposited), on a coating (e.g., on which a capping layer can be deposited), or on an underlayer.

[0178] Any useful substrate can be used, including any material construction suitable for lithographic processing, particularly for the production of integrated circuits and other semiconductor devices. In some embodiments, the substrate is a silicon wafer. The substrate can be a silicon wafer on which features with irregular surface topography ("underlying topographical features") are created.

[0179] Such underlying topographical features may include areas where material has been removed (e.g., by etching) or added (e.g., by deposition) during processing prior to performing the methods of the present technology. Such pre-processing may include the methods of the present technology or other processing methods by iterative processing whereby two or more layers of features are formed on the substrate. Without limiting the mechanism, function, or utility of the present technology, in some embodiments, the methods of the present technology are believed to offer advantages over, among other methods, methods that deposit photolithographic coatings on the surface of a substrate using spin-casting techniques. Such advantages may be due to the fact that the coatings of the present technology conform to underlying features without "filling" or otherwise planarizing such features, and that the coatings can be deposited on a wide variety of material surfaces.

[0180] In some embodiments, a next wafer can be prepared having a substrate surface of the desired material, with the topmost material being the layer to which the resist pattern is to be transferred. While material selection can vary depending on the integration level, it is generally desirable to select a material that can be etched with high selectivity to (i.e., much more quickly than) the EUV resist or imaging layer. Suitable substrate materials include various carbon-based coatings (e.g., ashable hard masks (AHMs)), silicon-based coatings (e.g., silicon, silicon oxide, silicon nitride, silicon oxynitride, or silicon oxycarbonitride, as well as SiO x , SiO x N y , SiO x C y N z , a-Si:H, poly-Si, or SiN, including their doped forms), or any other (generally sacrificial) coating applied to facilitate the patterning process.

[0181] In some embodiments, the substrate is a hard mask used in lithographic etching of the underlying semiconductor material. The hard mask may be formed of amorphous carbon (aC), SnO x, SiO2, SiO x N y , SiO x C, Si3N4, TiO2, TiN, W, W-doped C, WO x For example, the substrate may preferably be a SnO substrate, such as SnO. x In various embodiments, the layer may be 1 nm to 100 nm thick, or 2 nm to 10 nm thick.

[0182] In some non-limiting embodiments, the substrate includes an underlayer. The underlayer may be deposited on a hard mask or other layer and generally lies below the imaging layer (or coating) described herein. The underlayer may be used to improve the sensitivity of the PR, increase EUV absorption, and / or increase the patterning performance of the PR. If device features that create significant topography are present in the substrate to be patterned, another important function of the underlayer may be to overlay and planarize the existing topography so that subsequent patterning steps can be performed on a flat surface in all areas of the desired pattern. In such applications, the underlayer (or at least one of multiple underlayers) may be applied using a spin-coating technique. If the PR material being used has a significant inorganic component, e.g., exhibits a predominantly metal oxide framework, the underlayer may advantageously be a carbon-based coating applied by either spin-coating or a dry vacuum-based deposition process. The layers may include various ashable hardmask (AHM) coatings with carbon-based and hydrogen-based compositions, and may be doped with additional elements such as tungsten, boron, nitrogen, or fluorine.

[0183] In some embodiments, a surface activation operation may be used to activate the surface (e.g., of a substrate and / or coating) for future operations. For example, SiO xIn the case of surfaces, water or oxygen / hydrogen plasma may be used to create hydroxyl groups on the surface. In the case of carbon- or hydrocarbon-based surfaces, various treatments (e.g., water, hydrogen / oxygen, CO2 plasma, or ozone treatment) may be used to create carboxylic acid and / or hydroxyl groups. Such techniques may prove important for improving adhesion to the substrate of resist features that might otherwise delaminate or lift off in solvents during handling or development.

[0184] Adhesion can also be enhanced by introducing roughness into the surface to increase the surface area available for interaction, as well as by directly improving mechanical adhesion. For example, a sputtering process using Ar or other non-reactive ion bombardment can first be used to generate a rough surface. The surface can then be terminated with the desired surface functional groups (e.g., hydroxyl and / or carboxylic acid groups) as described above. For carbon, a combination approach can be used, using chemically reactive oxygen-containing plasmas such as CO2, O2, or H2O (or a mixture of H2 and O2) to etch away a thin layer of a coating with localized non-uniformities while simultaneously terminating it with -OH, -OOH, or -COOH groups. This can be done with or without a bias. In conjunction with the surface modification strategies mentioned above, this approach can serve the dual purpose of surface roughening and chemical activation of the substrate surface, either for direct adhesion to inorganic metal oxide-based resists or as an intermediate surface modification for further functionalization.

[0185] In various embodiments, the surface (e.g., of a substrate and / or coating) comprises exposed hydroxyl groups on its surface. Generally, the surface may be any surface that includes or has been treated to create exposed hydroxyl surfaces. Such hydroxyl groups may be formed on the surface by surface treatment of the substrate using oxygen plasma, water plasma, or ozone. In other embodiments, the surface of the coating may be treated to provide exposed hydroxyl groups, onto which a capping layer may be applied. In various embodiments, the hydroxyl-terminated metal oxide layer has a thickness of 0.1 nm to 20 nm, or 0.2 nm to 10 nm, or 0.5 nm to 5 nm.

[0186] EUV exposure processing EUV exposure of the coating can provide EUV-exposed regions with activated reaction centers containing a metal atom (M), generated by an EUV-mediated cleavage event. Such reaction centers can include dangling metal bonds, M-H groups, cleaved M-ligand groups, dimerized M-M bonds, or M-O-M crosslinks. In other embodiments, EUV exposure provides crosslinked organic moieties within the coating by photopolymerizing the ligand; or EUV exposure releases gaseous byproducts due to photolysis of bonds within the ligand.

[0187] The EUV exposure may have a wavelength in the range of about 10 nm to about 20 nm in a vacuum environment, such as a wavelength of 10 nm to 15 nm, e.g., 13.5 nm. In particular, patterning can provide EUV-exposed and EUV-unexposed regions to form a pattern.

[0188] The present techniques can include patterning using EUV, as well as DUV or electron beam. In such patterning, radiation is focused on one or more regions of the imaging layer. Exposure is typically performed so that the imaging layer coating includes one or more regions that are not exposed to radiation. The resulting imaging layer may include multiple exposed and unexposed regions, creating a pattern that corresponds to the creation of transistors or other features of a semiconductor device formed by adding or removing material from the substrate during subsequent substrate processing. EUV, DUV, and electron beam radiation methods and apparatuses useful herein include known methods and apparatuses.

[0189] In some EUV lithography techniques, an organic hard mask (e.g., a PECVD amorphous hydrogenated carbon ashable hard mask) is patterned using a photoresist process. During photoresist exposure, EUV radiation is absorbed by the resist and the underlying substrate, generating high-energy photoelectrons (e.g., about 100 eV), which in turn generate a cascade of low-energy secondary electrons (e.g., about 10 eV) that diffuse laterally a few nanometers. These electrons increase the extent of chemical reactions within the resist, thereby increasing EUV dose sensitivity. However, the secondary electron pattern, which is random in nature, overlaps with the optical image. This unwanted secondary electron exposure results in loss of resolution, observable line edge roughness (LER), and linewidth variations in the patterned resist. These defects are then reproduced in the patterned material during subsequent pattern-transfer etching.

[0190] Disclosed herein is a vacuum-integrated metal hardmask process and associated vacuum-integrated hardware that combines film formation (deposition / condensation) and optical lithography, resulting in significant improvements in EUV lithography (EUVL) performance, such as reduced line edge roughness.

[0191] In various embodiments described herein, a deposition (e.g., condensation) process (e.g., ALD or MOCVD performed in a PECVD tool such as a Lam Vector®) can be used to form a thin coating of a metal-containing coating, such as a photosensitive metal salt or metal-containing organic compound (organometallic compound), that exhibits strong absorption at EUV (e.g., wavelengths on the order of 10 nm to 20 nm), e.g., at the wavelength of an EUVL light source (e.g., 13.5 nm = 91.8 eV). This coating photodecomposes upon EUV exposure and forms a metal mask, a pattern transfer layer, during subsequent etching (e.g., in a conductor etching tool such as a Lam2300™ Kiyo®).

[0192] Following deposition, the thin EUV-patternable coating is patterned by exposure to a beam of EUV light, typically under a relatively high vacuum. For EUV exposure, the metal-containing coating is then deposited in a chamber integrated into the lithography platform (e.g., a wafer stepper such as the TWINSCAN® NXE:3300B platform supplied by ASML, Veldhoven, The Netherlands) and transferred under vacuum to prevent reaction prior to exposure. Integration with lithography tools is facilitated by the fact that EUVL also requires significant reduced pressure given the strong optical absorption of incident photons by ambient gases such as HO and O. In other embodiments, photosensitive metal coating deposition and EUV exposure may be performed in the same chamber.

[0193] Development processes include wet or dry development The EUV-exposed or unexposed regions can be removed by any useful development process. In one embodiment, the EUV-exposed regions may have activated reactive centers such as dangling metal bonds, M-H groups, or dimerized M-M bonds. In certain embodiments, M-M groups can be selectively removed by using one or more dry development processes (e.g., halide chemistry). In other embodiments, the M-M bonds can be selectively removed by using a wet development process, for example, using hot ethanol and water to form soluble M(OH) nBy providing groups, the EUV-exposed regions can be selectively removed. In yet other embodiments, the EUV-exposed regions are removed by using wet development (e.g., by using a positive developer) or dry development. In some embodiments, the EUV-unexposed regions are removed by using wet development (e.g., by using a negative developer) or dry development.

[0194] Dry development processes may include the use of halides, such as HCl- or HBr-based processes. While this disclosure is not limited to a particular theory or mechanism of action, it is understood that this approach leverages the chemical reactivity of dry-deposited EUV photoresist films with cleaning chemicals (e.g., HCl, HBr, and BCl3) to form volatile products using vapor or plasma. Dry-deposited EUV photoresist films can be removed at etch rates of up to 1 nm / sec. Rapid removal of dry-deposited EUV photoresist films with these chemistries is applicable to chamber cleaning, backside cleaning, bevel cleaning, and PR development. While films can be removed using vapors at various temperatures (e.g., HCl or HBr at temperatures above -10°C, or BCl3 at temperatures above 80°C), plasma can also be used to further accelerate or enhance reactivity.

[0195] Plasma treatments may include transformer-coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP) using known equipment and techniques. For example, treatments may be performed at pressures of >0.5 mTorr (e.g., 1 mTorr to 100 mTorr, etc.) and power levels of <1000 W (e.g., <500 W). Temperatures may be 30°C to 300°C (e.g., 30°C to 120°C) at a flow rate of 100 to 1000 standard cubic centimeters per minute (sccm), e.g., about 500 sccm, for 1 to 3000 seconds (e.g., 10 to 600 seconds).

[0196] When the halide reactant flow is a flow of hydrogen gas and halide gas, remote plasma / UV radiation is used to generate radicals from H and Cl and / or Br, and the hydrogen and halide radicals are flowed into the reaction chamber to contact the patterned EUV photoresist on the substrate layer of the wafer. Suitable plasma power may range from 100 W to 500 W without bias. These conditions are suitable for some processing reactors, such as the Kiyo etch tool available from Lam Research Corporation of Fremont, California, although it should be understood that a wider range of processing conditions may be used depending on the capacity of the processing reactor.

[0197] In a thermal development process, the substrate is exposed to a dry development chemical (e.g., a Lewis acid) in a vacuum chamber (e.g., an oven). A suitable chamber may include a vacuum line, a dry development hydrogen halide chemical gas (e.g., HBr, HCl) line, and a heater for temperature control. In some embodiments, the interior of the chamber may be coated with a corrosion-resistant coating, such as an organic polymer or inorganic coating. One such coating is polytetrafluoroethylene (PTFE, e.g., Teflon 1M). Such materials can be used in the thermal processes of the present disclosure without risk of removal by plasma exposure.

[0198] The process conditions for dry development may be a reactant flow of 100 sccm to 500 sccm (e.g., 500 sccm HBr or HCl), a temperature of -10°C to 120°C (e.g., -10°C), and a pressure of 1 mTorr to 500 mTorr (e.g., 300 mTorr) without plasma for a time of about 10 seconds to 1 minute depending on the photoresist coating and its composition and properties.

[0199] In various embodiments, the methods of the present disclosure combine all dry steps of deposition, formation, (EUV) lithography photopatterning, and dry development. In such a process, the substrate may be transferred directly to a dry development / etch chamber following photopatterning in an EUV scanner. Such a process may avoid the material and production costs associated with wet development. Dry processing also offers greater tunability and can result in additional CD control and / or scum removal.

[0200] In various embodiments, EUV photoresists containing some amount of metal, metal oxide, and organic components can be dry developed by heat, plasma (e.g., which may include photoactivated plasma, such as lamp heating or UV lamp heating), or a combination of heat and plasma methods while flowing a dry development gas containing a compound of the formula RxZy (where R = B, Al, Si, C, S, SO, x > 0, Z = Cl, H, Br, F, CH4, and y > 0). Dry development can result in a positive tone in which the RxZy species selectively remove the exposed material, leaving the unexposed counterpart behind as a mask. In some embodiments, exposed portions of organotin oxide-based photoresist coatings are removed by dry development in accordance with the present disclosure. Positive tone dry development may be achieved by selective dry development (removal) of the EUV exposed areas exposed to a flow containing hydrogen halide or halides including hydrogen and HCl and / or HBr without impinging plasma, or a flow of H and Cl and / or Br in which radicals are generated by a remote plasma or UV radiation generated from the plasma.

[0201] Wet development methods can also be used. In certain embodiments, such wet development methods are used to remove EUV-exposed regions to provide a positive-tone photoresist or a negative-tone resist. Exemplary, non-limiting wet development methods include those containing ammonium, e.g., alkaline developers (e.g., aqueous alkaline developers) such as ammonium hydroxide (NH4OH); ammonium-based ionic liquids, e.g., tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), or other quaternary alkylammonium hydroxides; mono-, di-, and tri-organic amines (e.g., , Ji In other embodiments, the alkaline developer may include the use of an organic amine such as ethylamine, ethylenediamine, triethylenetetramine; or an alkanolamine such as monoethanolamine, diethanolamine, triethanolamine, or diethyleneglycolamine. In other embodiments, the alkaline developer may include a nitrogen-containing base, such as a compound of formula R N1 NH2, R N1 R N2 N.H., R. N1 R N2 R N3 N or R N1 R N2 R N3 R N4 N + X N1- wherein R N1 , R N2 , R N3 , and R N4 each independently represents an organic substituent (e.g., an optionally substituted alkyl or any of those described herein) or two or more organic substituents which may be taken together; and X N1- OH - , F - , Cl - , Br - , I - or other quaternary ammonium cation species known in the art. Such bases may also include heterocyclyl nitrogen compounds, some of which are described herein.

[0202] Other development methods include the use of acidic developers (e.g., aqueous acidic developers or acidic developers in organic solvents) containing halides (e.g., HCl or HBr), organic acids (e.g., formic acid, acetic acid, or citric acid), or organic fluorine compounds (e.g., trifluoroacetic acid); or the use of organic developers, such as ketones (e.g., 2-heptanone, cyclohexanone, or acetone), esters (e.g., γ-butyrolactone or ethyl 3-ethoxypropionate (EEP)), alcohols (e.g., isopropyl alcohol (IPA)), or ethers such as glycol ethers (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA)), and combinations thereof.

[0203] In certain embodiments, the positive developer is an aqueous alkaline developer (e.g., containing NHOH, TMAH, TEAH, TPAH, or TBAH). In other embodiments, the negative developer is an aqueous acidic developer, an acidic developer in an organic solvent, or an organic developer (e.g., HCl, HBr, formic acid, trifluoroacetic acid, 2-heptanone, IPA, PGME, PGMEA, or a combination thereof).

[0204] Post-application treatment The methods herein may include any useful post-application treatments described below.

[0205] In backside and bevel cleaning processes, the vapor and / or plasma can be limited to specific areas of the wafer to ensure backside and bevel removal without degrading any coatings on the front side of the wafer. The dry-deposited EUV photoresist coatings being removed are typically composed of Sn, O, and C, but the same cleaning techniques can be extended to coatings of other metal oxide resists and materials. Additionally, this technique can be used for coating stripping and PR reformation.

[0206] Suitable process conditions for dry bevel edge and backside cleaning may be reactant flows of 100 sccm to 500 sccm (e.g., 500 sccm of HCl, HBr, or H and Cl or Br, BCl, or H), temperatures of -10°C to 120°C (e.g., 20°C), pressures of 20 mTorr to 500 mTorr (e.g., 300 mTorr), radio frequency (e.g., 13.56 MHz) plasma powers of 0 to 500 W, and times of about 10 seconds to 20 seconds, depending on the photoresist film and composition and properties. These conditions are suitable for some process reactors, e.g., Kiyo etch tools available from Lam Research Corporation of Fremont, California, although it should be understood that a wider range of process conditions may be used depending on the capacity of the process reactor.

[0207] Photolithography processing typically includes one or more bake steps to promote the chemical reactions necessary to create chemical contrast between exposed and unexposed areas of the photoresist. For high-volume manufacturing (HVM), such bake steps are typically performed in a track, with the wafer baked on a hotplate at a predetermined temperature under ambient air or, in some cases, under N flow. More careful control of the bake environment, as well as the introduction of additional reactive gas components into the environment during such bake steps, can further help reduce dose requirements and / or improve pattern fidelity.

[0208] According to various aspects of the present disclosure, one or more post-treatments on metal and / or metal oxide-based photoresists after deposition (e.g., post-apply bake (PAB)), exposure (e.g., post-exposure bake (PEB)), and / or development (e.g., post-develop bake (PDB)) can increase the material property difference between exposed and unexposed photoresist, thus reducing dose-to-size (DtS), improving PR profile, and improving line edge roughness and line width roughness (LER / LWR) after subsequent dry development. Such treatments may include thermal treatments with controlled temperature, gas environment, and moisture, which can result in improved dry development performance in subsequent processing. In some cases, remote plasma may be used.

[0209] For post-application processing (e.g., PAB), thermal treatments under controlled temperature, gas environment (e.g., air, HO, CO, CO, O, O, CH, CHOH, N, H, NH, NO, NO, Ar, He, or mixtures thereof) or vacuum, and moisture can be used after deposition and before exposure to alter the composition of unexposed metal and / or metal oxide photoresists. This alteration increases the EUV sensitivity of the material, thus achieving lower dose-to-size and edge roughness after exposure and dry development.

[0210] For post-exposure processing (e.g., PEB), thermal treatments under controlled temperature, gas atmosphere (e.g., air, HO, CO, CO, O, O, CH, CHOH, N, H, NH, NO, NO, Ar, He, or mixtures thereof), or vacuum, and moisture, can be used to change the composition of both the unexposed and / or exposed photoresist. This change can increase the compositional / material property difference between the unexposed and exposed photoresist, as well as the etch rate difference between the unexposed and exposed photoresist and dry development etch gases. This can achieve higher etch selectivity. Increased selectivity can result in a more squared PR profile with improved surface roughness and / or less photoresist residue / scum. In certain embodiments, PEB can be performed in air and, optionally, in the presence of moisture and CO.

[0211] For post-development treatments (e.g., post-develop bake or PDB), thermal treatments in which temperature, gas atmosphere (e.g., air, HO, CO, CO, O, O, CH, CHOH, N, H, NH, NO, NO, Ar, He, or mixtures thereof) or under vacuum (e.g., UV), and moisture are controlled can be used to alter the composition of the unexposed photoresist. In certain embodiments, conditions also include the use of plasma (e.g., including O, O, Ar, He, or mixtures thereof). This change can increase the hardness of the material, which can be beneficial if the film is to be used as a resist mask in etching an underlying substrate.

[0212] In such cases, in an alternative implementation, the thermal treatment can be replaced with a remote plasma treatment to increase the reactive species, lowering the energy barrier for the reaction and increasing productivity. Remote plasma can generate more reactive radicals, thus lowering the reaction temperature / time of the treatment, leading to increased productivity.

[0213] Therefore, one or more treatments may be applied to modify the photoresist itself to increase dry development selectivity. This thermal or radical modification can increase the contrast between unexposed and exposed materials, thus increasing the selectivity of the subsequent dry development step. The resulting material property difference between unexposed and exposed materials can be tailored by adjusting process conditions, including temperature, gas flow, moisture, pressure, and / or RF power. The greater process latitude enabled by dry development, which is not limited by material solubility in the wet developer solvent, allows for the application of more aggressive conditions, further enhancing the achievable material contrast. The resulting high material contrast feeds back into a wider process window for dry development, enabling increased productivity, lower costs, and better defect performance.

[0214] A significant limitation of wet-developable resist films is their limited bake temperature. Because wet development relies on material solubility, heating above, for example, 220°C, can significantly increase the degree of crosslinking in both exposed and unexposed regions of a metal-containing PR film, rendering both insoluble in the wet developer solution and making the film no longer reliably wet-developable. For example, for wet-spin-on or wet-developed metal-containing PR films, PAB, PEB, etc. bakes may be performed at temperatures below, for example, 180°C, 200°C, or 250°C. For dry-developed resist films where the etch rate difference between exposed and unexposed regions of the PR (i.e., selectivity) depends on removing only the exposed or unexposed portions of the resist, the PAB, PEB, or PDB processing temperature can be varied over a much wider window, e.g., about 90°C to 250°C, such as 90°C to 190°C, 90°C to 600°C, 100°C to 400°C, 125°C to 300°C, and about 170°C to 250°C or higher, such as 190°C to 240°C (e.g., for PAB, PEB, and / or PDB), to tune and optimize the treatment process. Decreased etch rates and improved etch selectivity have been found to occur at higher processing temperatures within the aforementioned ranges.

[0215] In certain embodiments, the PAB, PEB, and / or PDB processes may be performed with a gas environment flow ranging from 100 sccm to 10,000 sccm, a water content in an amount ranging from a few percent to 100% (e.g., 20% to 50%), a pressure between atmospheric pressure and vacuum, and a duration of about 1 to 15 minutes, e.g., about 2 minutes.

[0216] These findings can be used to adjust process conditions to tailor or optimize the process for specific materials and situations. For example, the selectivity achieved at a given EUV dose by a PEB thermal treatment at 220°C to 250°C for about 2 minutes in air with about 20% humidity can be similar to that achieved at EUV doses about 30% higher without such a thermal treatment. Thus, depending on the selectivity requirements / constraints of a semiconductor processing operation, thermal treatments such as those described herein can be used to lower the required EUV dose. Alternatively, if higher selectivity is required and a higher dose can be tolerated, up to 100x selectivity of exposed versus unexposed regions can be achieved, much higher than would be possible in wet development situations.

[0217] Still other steps can include in-situ metrology, which can evaluate physical and structural attributes (e.g., critical dimensions, coating thickness, etc.) during photolithography processing. Modules for implementing in-situ metrology can include, for example, scatterometry, ellipsometry, downstream mass spectrometry, and / or plasma-enhanced downstream optical emission spectroscopy modules.

[0218] Device The present disclosure also includes any apparatus configured to perform any of the methods described herein. In one embodiment, an apparatus for depositing a film includes a deposition module comprising a chamber for depositing an EUV-sensitive material as a film by providing a Ta-based precursor or other metal precursor in the optional presence of a counter reactant; a patterning module comprising an EUV photolithography tool having a source of sub-30 nm wavelength radiation; and a development module comprising a chamber for developing the film.

[0219] The apparatus may further include a controller having instructions for such modules. In one embodiment, the controller includes one or more memory elements, one or more processors, and system control software coded with instructions for performing film deposition. Such may include depositing a Ta-based precursor or other metal precursor as a film on the top surface of a substrate or photoresist layer, optionally with a reducing gas, alkyne, and / or counter reactant, in a deposition module; patterning the film directly with EUV exposure to sub-30 nm resolution, thereby forming a pattern in the film, in a patterning module; and developing the film in a development module. In certain embodiments, the development module provides removal of EUV-exposed or unexposed regions, thereby providing a pattern in the film.

[0220] 4 illustrates a schematic diagram of an embodiment of a processing station 400 having a processing chamber body 402 for maintaining a low-pressure environment suitable for implementing the strip and develop embodiments described herein. Multiple processing stations 400 may be included in a common low-pressure processing tool environment. For example, FIG. 5 illustrates an embodiment of a multi-station processing tool 500, such as a VECTOR® processing tool available from Lam Research Corporation of Fremont, California. In some embodiments, one or more hardware parameters of the processing stations 400, including those discussed in detail below, may be programmatically adjusted by one or more computer controllers 450.

[0221] The processing stations may be configured as modules in a cluster tool. Figure 7 illustrates a semiconductor processing cluster tool architecture having a vacuum-integrated deposition and patterning module suitable for implementing embodiments described herein. Such a cluster processing tool architecture may include a resist deposition module, a resist exposure (EUV scanner) module, a resist dry develop module, and an etch module as described herein with reference to Figures 6 and 7.

[0222] In some embodiments, certain processing functions, such as dry developing and etching, can be performed sequentially in the same module. Embodiments of the present disclosure also relate to methods and apparatus for receiving a wafer including a photo-patterned EUV resist thin coat layer disposed on a layer or layer stack to be etched into a development / etch chamber (e.g., a dry development / etch chamber or a wet development / etch chamber) after photo-patterning in an EUV scanner; for developing the photo-patterned EUV resist thin coat layer; and for then etching an underlying layer using the patterned EUV resist as a mask as described herein.

[0223] Returning to FIG. 4 , the processing station 400 is in fluid communication with a reactant delivery system 401 a for delivering process gases to a distribution showerhead 406 via connection 405. The reactant delivery system 401 a optionally includes a mixing vessel 404 for formulating and / or preparing the process gases for delivery to the showerhead 406. One or more mixing vessel inlet valves 420 may control the introduction of process gases into the mixing vessel 404. Also, if plasma exposure is used, the plasma may be delivered to the showerhead 406 or generated in the processing station 400. The process gas may include any of those described herein, such as, for example, a Ta-based precursor, a Sn-based precursor, a metal precursor, a reducing gas, an alkyne, a hydrocarbon, a counter reactant, or an inert gas.

[0224] 4 includes an optional vaporization point 403 for vaporizing a liquid reactant supplied to the mixing vessel 404. The liquid reactant may include a metal precursor (e.g., a Ta-based precursor and / or a Sn-based precursor) or a counter reactant. In some embodiments, a liquid flow controller (LFC) may be provided upstream of the vaporization point 403 to control the mass flow rate of the liquid for vaporization and delivery to the processing station 400. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. A plunger valve of the LFC may then be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM.

[0225] The showerhead 406 distributes process gases toward the substrate 412. In the embodiment depicted in Figure 4, the substrate 412 is shown positioned directly below the showerhead 406 and resting on a pedestal 408. The showerhead 406 may have any suitable number and arrangement of ports for distributing process gases to the substrate 412.

[0226] In some embodiments, the pedestal 408 may be raised or lowered to expose the substrate 412 to the volume between the substrate 412 and the showerhead 406. It will be appreciated that in some embodiments, the height of the pedestal may be programmatically adjusted by a suitable computer controller 450.

[0227] In some embodiments, the pedestal 408 may be temperature controlled by a heater 410. In some embodiments, the pedestal 408 may be heated to a temperature greater than 0° C. up to 300° C. or higher, for example, between 50° C. and 120° C., such as between about 65° C. and 80° C., during non-plasma thermal exposure of the photopatterned resist to dry developing chemistries such as HBr, HCl, or BCl3, as described in embodiments of the present disclosure.

[0228] Additionally, in some embodiments, pressure control of the processing station 400 may be provided by a butterfly valve 418. As shown in the embodiment of Figure 4, the butterfly valve 418 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of the processing station 400 may also be adjusted by varying the flow rate of one or more gases introduced to the processing station 400.

[0229] In some embodiments, the position of the showerhead 406 relative to the pedestal 408 may be adjusted to vary the volume between the substrate 412 and the showerhead 406. Furthermore, it will be appreciated that the vertical position of the pedestal 408 and / or the showerhead 406 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 408 may include a rotation axis for rotating the orientation of the substrate 412. It will be appreciated that in some embodiments, one or more of these exemplary adjustments may be implemented programmatically by one or more suitable computer controllers 450.

[0230] For example, in embodiments where plasma may be used for gentle plasma-based dry development and / or etching operations performed in the same chamber, the showerhead 406 and pedestal 408 are in electrical communication with a radio frequency (RF) power source 414 and matching network 416 for powering the plasma 407. In some embodiments, the plasma energy may be controlled by controlling one or more of the process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power source 414 and matching network 416 may be operated at any suitable power to form a plasma having a desired composition of radical species. An example of a suitable power is up to about 500 W.

[0231] In some embodiments, instructions for the controller 450 may be provided by input / output control (IOC) sequence instructions. In one example, instructions for setting conditions for a process step may be included in a corresponding recipe step of a process recipe. In some cases, process recipe steps may be arranged sequentially such that all instructions for a process step are executed simultaneously with that process step. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe step. For example, a recipe step may include instructions for setting a flow rate of a dry development chemical reactant gas, such as HBr or HCl, and a time delay instruction for the recipe step. In some embodiments, the controller 450 may include any of the functionality described below with respect to the system controller 550 of FIG. 5.

[0232] As described above, one or more processing stations may be included in a multi-station processing tool. Figure 5 shows a schematic diagram of an embodiment of a multi-station processing tool 500 having an entry load lock 502 and an exit load lock 504, either or both of which may be equipped with a remote plasma source. An atmospheric robot 506 is configured to move wafers from a cassette loaded via a pod 508 to the entry load lock 502 through an atmospheric port 510. The wafer is placed on a pedestal 512 of the entry load lock 502 by the robot 506, the atmospheric port 510 is closed, and the load lock is evacuated. If the entry load lock 502 is equipped with a remote plasma source, the wafer may be exposed to a remote plasma treatment in the load lock to treat the silicon nitride surface before being introduced into the processing chamber 514. Furthermore, the wafer may also be heated in the entry load lock 502 to remove, for example, moisture and adsorbed gases. The chamber transfer port 516 to the processing chamber 514 is then opened and another robot (not shown) places the wafer on the pedestal of the first station shown in the reactor for processing. While the embodiment shown in Figure 5 includes a load lock, it will be understood that some embodiments may provide for direct wafer entry into the processing stations.

[0233] The illustrated processing chamber 514 includes four processing stations, numbered 1 through 4, in the embodiment shown in FIG. 5 . Each station has a heated pedestal (station 1 is shown as 518) and a gas line inlet. It will be understood that in some embodiments, each processing station may have different or multiple purposes. For example, in some embodiments, a processing station may be switchable between a dry development mode and an etch processing mode. Additionally or alternatively, in some embodiments, the processing chamber 514 may include one or more corresponding pairs of dry development and etch processing stations. While the illustrated processing chamber 514 includes four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, the processing chamber may have five or more stations, and in other embodiments, the processing chamber may have three or fewer stations.

[0234] FIG. 5 illustrates an embodiment of a wafer handling system 590 for transferring wafers within the processing chamber 514. In some embodiments, the wafer handling system 590 may transfer wafers between various processing stations and / or between processing stations and load locks. It will be understood that any suitable wafer handling system may be used. Non-limiting examples include a wafer carousel and a wafer handling robot. FIG. 5 also illustrates an embodiment of a system controller 550 used to control the processing conditions and hardware states of the processing tool 500. The system controller 550 may include one or more memory devices 556, one or more mass storage devices 554, and one or more processors 552. The processor 552 may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0235] In some embodiments, the system controller 550 controls all of the activities of the processing tool 500. The system controller 550 executes system control software 558 stored on the mass storage device 554, loaded into the memory device 556, and executed by the processor 552. Alternatively, the control logic may be hard-coded into the controller 550. Application-specific integrated circuits, programmable logic devices (e.g., field-programmable gate arrays, or FPGAs), or the like may be used for this purpose. In the following discussion, whenever "software" or "code" is used, functionally equivalent hard-coded logic may be used instead. The system control software 558 may include the timing, mixture of gases, gas flow rates, chamber and / or station pressure, chamber and / or station temperature, wafer temperature, target power levels, RF power levels, substrate pedestal, chuck and / or susceptor position, and other parameters of a particular process being performed by the processing tool 500. The system control software 558 may be configured in any suitable manner. For example, various processing tool component subroutines or control objects may be written to control the operation of processing tool components used to perform various processing processes. The system control software 558 may be coded in any suitable computer-readable programming language.

[0236] In some embodiments, the system control software 558 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. Some embodiments may use other computer software and / or programs stored on the mass storage device 554 and / or memory devices 556 associated with the system controller 550. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0237] The substrate positioning program may include program code for processing tool components used to load the substrate onto the pedestal 518 and control the spacing between the substrate and other parts of the processing tool 500 .

[0238] The process gas control program may include code for controlling various gas compositions (e.g., HBr or HCl gas as described herein) and flow rates, and optionally code for flowing gases to one or more process stations prior to deposition to stabilize the pressure of the process stations. The pressure control program may include code for controlling the pressure of the process stations, for example, by adjusting throttle valves in the exhaust systems of the process stations, gas flows to the process stations, etc.

[0239] The heater control program may include code for controlling the current to a heating unit used to heat the substrate. Alternatively, the heater control program may control the delivery of a heat transfer gas (such as helium) to the substrate.

[0240] The plasma control program may include code for setting RF power levels applied to the process electrodes of one or more process stations in accordance with embodiments herein.

[0241] The pressure control program may include code for maintaining the pressure in the reaction chamber according to embodiments herein.

[0242] In some embodiments, there may be a user interface associated with the system controller 550. The user interface may include a display screen, a graphical software display of equipment status and / or processing conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0243] In some embodiments, the parameters adjusted by the system controller 550 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF bias power levels), etc. Such parameters may be provided to the user in the form of a recipe, which may be entered using a user interface.

[0244] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 550 from various process tool sensors. Signals for controlling the process may be output at analog and digital output connections of the process tool 500. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used in conjunction with data from such sensors to maintain process conditions.

[0245] The system controller 550 may provide program instructions for implementing the deposition processes described above. The program instructions may control various process parameters, such as DC power levels, RF bias power levels, pressure, temperature, etc. The instructions may control parameters for operating dry development and / or etching processes according to various embodiments described herein.

[0246] The system controller 550 will typically include one or more memory elements and one or more processors configured to execute instructions such that the device performs methods according to embodiments of the present disclosure. A machine-readable medium containing instructions for controlling processing operations according to embodiments of the present disclosure may be coupled to the system controller 550.

[0247] In some implementations, the system controller 550 is part of a system that may be part of the examples described above. Such a system may include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (such as a wafer pedestal or gas flow system). Such systems may be integrated with electronics for controlling operations before, during, and after processing of semiconductor wafers or substrates. The electronics may be referred to as a "controller," and the controller may control various components or subcomponents of one or more systems. The system controller 550 may be programmed to control any of the processes disclosed herein, including delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer into and out of tools and other transfer tools and / or load locks connected or interfaced with a particular system, depending on the processing conditions and / or type of system.

[0248] Generally, system controller 550 may be defined as electronic equipment having various integrated circuits, logic, memory, and / or software for receiving instructions, issuing instructions, controlling operations, enabling cleaning operations, enabling endpoint measurements, etc. Integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application-specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). Program instructions may be in the form of various individual settings (or program files) communicated to system controller 550 and define operational parameters for performing a particular process on or with a semiconductor wafer or system. The operational parameters, in some embodiments, may be part of a recipe defined by a process engineer to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0249] In some implementations, the system controller 550 may be part of or connected to a computer that is integrated into or otherwise networked with the system, or a combination thereof. For example, the system controller 550 may reside in the “cloud” and be all or part of a manufacturing host computer system that can enable remote access of wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, examine the history of past manufacturing operations, and examine trends or performance indicators from multiple manufacturing operations to change parameters of a current process, configure processing steps following a current process, or initiate a new process. In some examples, a remote computer (e.g., a server) can provide process recipes to the system over a network, which may include a local network or the Internet. The remote computer may include a user interface that allows entry or programming of parameters and / or settings that are subsequently communicated to the system from the remote computer. In some examples, the system controller 550 receives instructions in the form of data specifying parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool the system controller 550 is configured to interface with or control. Thus, as described above, the system controller 550 may be distributed, such as by comprising one or more separate controllers networked together to serve a common purpose, such as the processing and control described herein. An example of a distributed controller for such a purpose would be one or more integrated circuits located in the chamber that communicate with one or more remotely located integrated circuits (e.g., at the platform level or as part of a remote computer) that are combined to control processing in the chamber.

[0250] Without limitation, exemplary systems may include a plasma etch chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, an EUV lithography chamber (scanner) or module, a dry development chamber or module, and any other semiconductor processing system that may be associated with or used in the fabrication and / or manufacturing of semiconductor wafers.

[0251] As mentioned above, depending on the processing step or steps being performed by the tool, the system controller 550 may communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, another controller, or tools used for material transfer to carry containers of wafers between tool locations and / or load ports in a semiconductor fabrication factory.

[0252] In one particular embodiment, an inductively coupled plasma (ICP) reactor will now be described which may be suitable for etching operations suitable for implementing some embodiments. Although an ICP reactor is described herein, it should be understood that in some embodiments, a capacitively coupled plasma reactor may also be used.

[0253] 6 shows a schematic cross-sectional view of an inductively coupled plasma apparatus 600 suitable for implementing certain embodiments or aspects of embodiments, such as dry development and / or etching; an example of such an apparatus is the Kiyo® reactor produced by Lam Research Corp. of Fremont, Calif. In other embodiments, other tools or tool types capable of performing the dry development and / or etching processes described herein may be used for implementation.

[0254] The inductively coupled plasma apparatus 600 includes an overall processing chamber structurally defined by a chamber wall 601 and a window 611. The chamber wall 601 may be fabricated from stainless steel or aluminum. The window 611 may be fabricated from quartz or other dielectric materials. An optional internal plasma grid 650 divides the overall process chamber into an upper subchamber 602 and a lower subchamber 603. In most embodiments, the plasma grid 650 may be removed, thereby utilizing the chamber space comprised of the subchambers 602 and 603. A chuck 617 is positioned within the lower subchamber 603 near the bottom inner surface. The chuck 617 is configured to receive and hold a semiconductor wafer 619 on which etching and deposition processes are performed. The chuck 617 may be an electrostatic chuck for supporting the wafer 619, if present. In some embodiments, an edge ring (not shown) surrounds the chuck 617 and, when present above the chuck 617, has an upper surface that is in a generally planar relationship with the top surface of the wafer 619. The chuck 617 also includes an electrostatic electrode for chucking and dechucking the wafer 619. A filter and DC clamp power supply (not shown) may be provided for this purpose.

[0255] Other control systems may also be provided for lifting the wafer 619 from the chuck 617. The chuck 617 may be charged using an RF power supply 623. The RF power supply 623 is connected to a matching network 621 via connection 627. The matching network 621 is connected to the chuck 617 via connection 625. The RF power supply 623 is thus connected to the chuck 617. In various embodiments, the bias power of the electrostatic chuck may be set to about 50 V or may be set to a different bias power depending on the process being performed in accordance with embodiments of the present disclosure. For example, the bias power may be about 20 V to about 100 V or about 30 V to about 150 V.

[0256] The elements for plasma generation include a coil 633 positioned above the window 611. In some embodiments, a coil is not used in embodiments of the present disclosure. The coil 633 is fabricated from a conductive material and includes at least one full turn. The example coil 633 shown in FIG. 6 includes three turns. A cross section of the coil 633 is indicated with symbols, with the coil having an "x" rotating toward the page and the coil having a "●" rotating toward the page. The elements for plasma generation also include an RF power supply 641 configured to provide RF power to the coil 633. Generally, the RF power supply 641 is connected to a matching network 639 via connection 645. The matching network 639 is connected to the coil 633 via connection 643. The RF power supply 641 is thus connected to the coil 633. An optional Faraday shield 649 is positioned between the coil 633 and the window 611. The Faraday shield 649 may be maintained in a spatially spaced relationship relative to the coil 633. In some embodiments, the Faraday shield 649 is positioned directly above the window 611. In some embodiments, the Faraday shield resides between the window 611 and the chuck 617. In some embodiments, the Faraday shield is not maintained in a spatially spaced relationship to the coil 633. For example, the Faraday shield may reside directly below the window without being spaced apart. The coil 633, the Faraday shield 649, and the window 611 are each configured to be substantially parallel to one another. The Faraday shield 649 may prevent metals or other species from depositing on the window 611 of the processing chamber.

[0257] Process gases may enter the processing chamber through one or more main gas flow inlets 660 positioned in the upper subchamber 602 and / or through one or more side gas flow inlets 670. Similarly, although not explicitly shown, similar gas flow inlets may be used to supply process gases to the capacitively coupled plasma processing chamber. A vacuum pump, e.g., a one- or two-stage mechanical dry pump and / or turbomolecular pump 640, may be used to draw process gases from the processing chamber and maintain pressure within the processing chamber. For example, the vacuum pump may be used to evacuate the lower subchamber 603 during an ALD purge operation. A valve-controlled conduit may be used to fluidly connect the vacuum pump to the processing chamber to selectively control application of the vacuum environment provided by the vacuum pump. This may be accomplished using a closed-loop controlled flow restriction device, such as a throttle valve (not shown) or a pendulum valve (not shown), during plasma processing operations. Similarly, a vacuum pump and a valve-controlled fluid connection to the capacitively coupled plasma processing chamber may also be used.

[0258] During operation of the apparatus 600, one or more process gases may be supplied through the gas flow inlets 660 and / or 670. In certain embodiments, process gases may be supplied only through the main gas flow inlet 660 or only through the side gas flow inlet 670. In some cases, the gas flow inlets shown may be replaced with more complex gas flow inlets, such as one or more showerheads. The Faraday shield 649 and / or the optional grid 650 may include internal channels and holes that allow delivery of process gases to the processing chamber. Either or both the Faraday shield 649 and the optional grid 650 may function as showerheads for delivering process gases. In some embodiments, a liquid vaporization and delivery system may be located upstream of the processing chamber such that once a liquid reactant or precursor is vaporized, the vaporized reactant or precursor is introduced into the processing chamber through the gas flow inlets 660 and / or 670.

[0259] Radio frequency power is supplied from RF power supply 641 to coil 633, causing an RF current to flow through coil 633. The RF current flowing through coil 633 generates an electromagnetic field around coil 633. The electromagnetic field generates an induced current within upper subchamber 602. Physical and chemical interactions of the various generated ions and radicals with wafer 619 etch features in wafer 619 and selectively deposit layers on wafer 619.

[0260] When a plasma grid 650 is used such that both an upper subchamber 602 and a lower subchamber 603 are present, the induced current acts on the gas present in the upper subchamber 602 to generate an electron-ion plasma in the upper subchamber 602. The optional internal plasma grid 650 confines the amount of hot electrons within the lower subchamber 603. In some embodiments, the apparatus 600 is designed and operates such that the plasma present in the lower subchamber 603 is an ion-ion plasma.

[0261] Both the upper electron-ion plasma and the lower ion-ion plasma may contain positive and negative ions, but the ion-ion plasma will have a higher ratio of negative ions to positive ions. Volatile etching and / or deposition byproducts may be removed from the lower subchamber 603 via port 622. The chuck 617 disclosed herein may operate at elevated temperatures ranging from about 10° C. to about 250° C. The temperature will depend on the processing operation and the particular recipe.

[0262] The tool 600 may be connected to equipment (not shown) when installed in a clean room or manufacturing facility. The equipment includes plumbing to provide process gases, vacuum, temperature control, and environmental particle control. Such equipment will be connected to the tool 600 when installed in the target manufacturing facility. Additionally, the tool 600 may be connected to a transfer chamber that allows robotic equipment to transfer semiconductor wafers in and out of the tool 600 using typical automation.

[0263] In some embodiments, a system controller 630 (which may include one or more physical or logic controllers) controls some or all of the operation of the processing chamber. The system controller 630 may include one or more memory devices and one or more processors. In some embodiments, the apparatus 600 includes a switching system for controlling flow rates and durations when embodiments of the present disclosure are implemented. In some embodiments, the apparatus 600 may have a switching time of up to about 600 ms, or up to about 750 ms. The switching time may depend on the flow chemistry, the selected recipe, the reactor architecture, and other factors.

[0264] In some implementations, the system controller 630 is part of a system that may be part of the examples described above. Such a system may include semiconductor processing equipment with one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (such as a wafer pedestal, a gas flow system, etc.). Such systems may be integrated with electronics for controlling pre-, during-, and post-processing operations of semiconductor wafers or substrates. The electronics may be integrated into the system controller 630, which may control various components or subcomponents of one or more systems. The system controller may be programmed to control any of the processes disclosed herein, including delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer into and out of tools and other transfer tools and / or load locks connected or interfaced with the specific system, depending on the process parameters and / or type of system.

[0265] Generally, the system controller 630 may be defined as electronic equipment having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application-specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). The program instructions may be communicated to the controller in the form of various individual settings (or program files) and may be instructions that define operational parameters for performing a particular process on or with respect to a semiconductor wafer or system. The operational parameters, in some embodiments, may be part of a recipe defined by a process engineer to accomplish one or more processing steps during the fabrication or removal of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or die of a wafer.

[0266] In some implementations, the system controller 630 may be part of or connected to a computer that is integrated into the system, connected to the system, otherwise networked with the system, or a combination thereof. For example, the controller may reside in the “cloud” or be all or part of a manufacturing host computer system that can enable remote access of wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, examine the history of past manufacturing operations, and examine trends or performance indicators from multiple manufacturing operations to change parameters of a current process, configure processing steps following a current process, or initiate a new process. In some examples, a remote computer (e.g., a server) can provide process recipes to the system over a network, which may include a local network or the Internet. The remote computer may include a user interface that allows entry or programming of parameters and / or settings that are subsequently communicated to the system from the remote computer. In some examples, the system controller 630 receives instructions in the form of data specifying parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool the controller is configured to interface with or control. Thus, as described above, the system controller 630 may be distributed, such as by comprising one or more separate controllers networked together to serve a common purpose, such as the processing and control described herein. An example of a distributed controller for such a purpose would be one or more integrated circuits located in the chamber that communicate with one or more remotely located integrated circuits (e.g., at the platform level or as part of a remote computer) that are combined to control processing in the chamber.

[0267] Without limitation, exemplary systems may include a plasma etch chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an ALE chamber or module, an ion implantation chamber or module, a track chamber or module, an EUV lithography chamber (scanner) or module, a dry development chamber or module, and any other semiconductor processing system that may be associated with or used in the processing and / or manufacturing of semiconductor wafers.

[0268] As described above, depending on the processing step or steps being performed by the tool, the controller may communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, another controller, or tools used for material transfer to carry containers of wafers between tool locations and / or load ports in a semiconductor fabrication factory.

[0269] EUVL patterning may be performed using any suitable tool, often referred to as a scanner, such as the TWINSCAN NXE:3300B® platform supplied by ASML, Veldhoven, The Netherlands. The EUVL patterning tool may be a stand-alone device that loads and unloads substrates for deposition and etching, as described herein. Alternatively, as described below, the EUVL patterning tool may be a module of a larger, multi-component tool. FIG. 7 illustrates a semiconductor processing cluster tool architecture having a vacuum-integrated deposition module, EUV patterning module, and dry develop / etch module interfaced with a vacuum transfer module, suitable for implementing the processes described herein. The processes may also be performed without such a vacuum-integrated device, which may be advantageous in some implementations.

[0270] 7 illustrates a semiconductor processing cluster tool architecture having vacuum-integrated deposition and patterning modules interfaced with a vacuum transfer module suitable for implementing the processes described herein. The configuration of transfer modules for "transferring" wafers between multiple storage facilities and processing modules may be referred to as a "cluster tool architecture" system. The deposition and patterning modules are vacuum-integrated depending on the requirements of the particular process. Other modules, such as for etching, may also be included in the cluster.

[0271] A vacuum transfer module (VTM) 738 interfaces with four processing modules 720a-720d, each of which may be individually optimized to perform various manufacturing processes. By way of example, processing modules 720a-720d may be implemented to perform deposition, evaporation, ELD, dry development, etching, stripping, and / or other semiconductor processes. For example, module 720a may be an ALD reactor that may operate to perform the non-plasma thermal atomic layer deposition described herein, such as a Vector tool available from Lam Research Corporation of Fremont, California. Additionally, module 720b may be a PECVD tool, such as a Lam Vector®. It should be understood that the figures are not necessarily drawn to scale.

[0272] Airlocks 742 and 746, also known as load locks or transfer modules, interface with VTM 738 and patterning module 740. For example, as mentioned above, a suitable patterning module may be a TWINSCAN® NXE:3300B platform supplied by ASML of Veldhoven, The Netherlands. This tool architecture allows workpieces, such as semiconductor substrates or wafers, to be transferred under vacuum to prevent reaction prior to exposure. Integration of the deposition module with the lithography tool is facilitated by the fact that EUVL also requires significant reduced pressure given the strong optical absorption of incident photons by ambient gases such as HO and O.

[0273] As mentioned above, this integrated architecture is only one possible embodiment of a tool for implementing the described process. The process may also be implemented using a stand-alone EUVL scanner and a deposition reactor, such as the Lam Vector tool described with reference to Figure 7, but which does not have an integrated patterning module, either stand-alone or integrated into a cluster architecture with other tools (such as the Lam Kiyo or Gamma tools) as etch, strip, etc. modules.

[0274] Airlock 742 may be an "outgoing" load lock, referring to the transfer of substrates from VTM 738, which serves as deposition module 720a, to patterning module 740, and airlock 746 may be an "incoming" load lock, referring to the transfer of substrates from patterning module 740 back to VTM 738. Incoming load lock 746 may also provide an interface to the outside of the tool for the transfer of substrates. Each processing module has a plane that interfaces the module to VTM 738. For example, deposition processing module 720a has plane 736. Sensors within each plane, such as sensors 1-18 shown, are used to detect the passage of wafer 726 as it moves between its respective stations. Similarly, patterning module 740 and airlocks 742 and 746 may be equipped with additional planes and sensors, not shown.

[0275] The main VTM robot 722 transfers wafers 726 between modules, including airlocks 742 and 746. In one embodiment, the robot 722 has one arm, and in another embodiment, the robot 722 has two arms, each arm having an end effector 724 for picking up a wafer, such as wafer 726, for transfer. The front-end robot 744 is used to transfer wafers 726 from the output airlock 742 to the patterning module 740 and from the patterning module 740 to the input airlock 746. The front-end robot 744 may also transfer wafers 726 between the input load lock and the exterior of the tool for substrate loading and unloading. The input airlock module 746 has the ability to match environments between atmospheric pressure and vacuum, allowing wafers 726 to move between the two pressure environments without damage.

[0276] It should be noted that EUVL tools typically operate at a higher vacuum than deposition tools. In that case, it may be desirable to increase the vacuum environment of the substrate during transfer between the deposition and EUVL tools to allow the substrate to be degassed before entering the patterning tool. The unloading airlock 742 may provide this function by holding the transferred wafer for a period of time at a lower pressure, no higher than the pressure in the patterning module 740, and evacuating any off-gassing, so that the optical components of the patterning module 740 are not contaminated by off-gassing from the substrate. A preferred pressure for the off-gas exhaust airlock is 1E-8 Torr or less.

[0277] In some embodiments, a system controller 750 (which may include one or more physical or logic controllers) controls some or all of the operation of the cluster tool and / or its individual modules. Note that the controller may be local to the cluster architecture, located on the manufacturing floor outside the cluster architecture, or may be remotely connected to the cluster architecture via a network. The system controller 750 may include one or more memory elements and one or more processors. The processor may include a central processing unit (CPU) or computer, analog and / or digital input / output connections, stepper motor controller boards, and other similar components. Instructions for implementing appropriate control operations are executed by the processor. Such instructions may be stored in memory elements associated with the controller or provided over a network. In certain embodiments, the system controller executes system control software.

[0278] The system control software may include instructions for controlling the timing of deposition and / or magnitude of any aspect of tool or module operation. The system control software may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be written to control the operation of process tool components necessary to perform various processing tool operations. The system control software may be coded in any suitable computer-readable programming language. In some embodiments, the system control software includes input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each stage of a semiconductor manufacturing process may include one or more instructions executed by the system controller. Instructions for setting process conditions for condensation, deposition, deposition, patterning, and / or etching stages, for example, may be included in the corresponding recipe stages.

[0279] In various embodiments, an apparatus for forming a negative pattern mask is provided. Such an apparatus may include a process chamber for patterning, depositing, and etching, and a controller including instructions for forming the negative pattern mask. The instructions may include code for patterning features in a chemically amplified (CAR) resist of a semiconductor substrate in the process chamber by EUV exposure to expose a surface of the substrate, dry developing the photo-patterned resist, and etching an underlying layer or layer stack using the patterned resist as a mask.

[0280] It should be noted that the computer controlling the wafer movement may be local to the cluster architecture, or may be located on the manufacturing floor outside the cluster architecture, or may be at a remote location and connected to the cluster architecture via a network.

[0281] conclusion Although the foregoing embodiments have been described in some detail for clarity of understanding, it will be apparent that certain changes and modifications can be made within the scope of the appended claims. The embodiments disclosed herein may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the embodiments of the present disclosure. Furthermore, while the embodiments of the present disclosure will be described in conjunction with specific embodiments, it will be understood that the specific embodiments are not intended to limit the embodiments of the present disclosure. It should be noted that there are numerous alternative ways to implement the processes, systems, and apparatus of the present embodiments. Therefore, the present embodiments should be considered illustrative and not limiting, and the embodiments should not be limited to the details set forth herein. The present disclosure includes the following application examples: [Application example 1] a semiconductor substrate having an upper surface; a patterned radiation sensitive coating disposed on the top surface of the semiconductor substrate; Including, The laminate, wherein the coating comprises tantalum and tin. [Application example 2] A laminate according to Application Example 1, wherein the patterning radiation-sensitive coating comprises an extreme ultraviolet (EUV)-sensitive coating. [Application example 3] 3. The stack according to claim 2, wherein the patterned radiation-sensitive coating comprises a mixed organometallic coating containing tantalum and tin. [Application example 4] 3. The stack of claim 2, wherein the patterned radiation-sensitive coating comprises a tantalum-containing layer disposed on a top surface or a bottom surface of a tin-containing layer. [Application example 5] The laminate according to Application Example 2, wherein the patterned radiation-sensitive coating has a thickness of about 5 nm to about 40 nm. [Application Example 6] 1. A method for forming a coating, comprising: depositing a tantalum-based precursor on a surface of a substrate to provide a patterned radiation-sensitive coating; Including, The method, wherein the tantalum-based precursor comprises a patterned radiation-sensitive moiety. [Application Example 7] The method according to Application Example 6, wherein the patterning radiation-sensitive coating comprises an extreme ultraviolet (EUV)-sensitive coating. [Application Example 8] The method according to Application Example 7, wherein the patterning radiation-sensitive moiety of the tantalum-based precursor comprises an EUV-labile group. [Application Example 9] The method according to Application Example 7, wherein the tantalum-based precursor is represented by the formula (I): TaR b L c (I) and During the ceremony, each R is independently an EUV labile group, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted imino, or optionally substituted alkylene; each L is independently a ligand or other moiety that is reactive with a reducing gas or acetylene; b≧0; and c≧1; method. [Application Example 10] The method according to Application Example 9, wherein the tantalum-based precursor is represented by formula (IA): R=Ta(L) b (IA) and During the ceremony, R = NR i or =CR i R ii and Each L is independently halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or a divalent ligand bonded to Ta, said divalent ligand being -NR i -Ak-NR ii - and Each R i and R ii are independently H, optionally substituted linear alkyl, optionally substituted branched alkyl, or optionally substituted cycloalkyl; Ak is optionally substituted alkylene or optionally substituted alkenylene; b≧1, method. [Application Example 11] The method according to any one of Application Examples 7 to 10, wherein the patterned radiation-sensitive coating comprises a tantalum nitride coating. [Application Example 12] The method according to any one of Aspects 7 to 10, wherein the film formation further includes an organometallic compound, and the tantalum-based precursor and the organometallic compound can be formed into a film together. [Application Example 13] The method according to Application Example 12, wherein the deposition further comprises adjusting the relative amounts of the tantalum-based precursor and the organometallic compound deposited in the coating. [Application Example 14] The method according to Application Example 13, wherein the adjusting includes changing the flow rates and / or deposition times of the tantalum-based precursor and the organometallic compound. [Application Example 15] In the method according to Application Example 12, the film formation is performed by: depositing the tantalum-based precursor and the organometallic compound in the optional presence of a reducing gas or acetylene, thereby providing the patterned radiation-sensitive coating comprising a mixed organometallic coating having two or more different metals. [Application Example 16] The method of Application Example 15, wherein the organometallic compound includes a tin-based precursor and the mixed organometallic coating includes tantalum and tin. [Application Example 17] The method according to Application Example 15, wherein the deposition comprises deposition by chemical vapor deposition at a temperature below about 250°C or below about 100°C. [Application Example 18] The method according to any one of Aspects 7 to 10, wherein the film formation further includes an organometallic compound, and the tantalum-based precursor and the organometallic compound can be successively formed into films in sequence. [Application Example 19] The method according to Application Example 18, wherein the sequence includes depositing the tantalum-based precursor and subsequently or prior to depositing the organometallic compound. [Application Example 20] The method described in Application Example 18, wherein the deposition further comprises adjusting the number or order of the sequence of the tantalum-based precursor and the organometallic compound that follows or precedes it. [Application Example 21] The method according to Application Example 18, The film formation is depositing said organometallic compound in the optional presence of a counter reactant in a chamber, thereby providing an organometallic-containing layer; purging the chamber with a purge gas; depositing the tantalum-based precursor in the chamber, thereby providing a tantalum-containing layer disposed on an upper surface of the organometallic-containing layer; purging the chamber with another purge gas; and exposing the tantalum-containing layer to a reducing gas or acetylene; A method comprising: [Application Example 22] 22. The method of claim 21, wherein the organometallic compound includes a tin-based precursor and the organometallic-containing layer includes tin. [Application Example 23] The method according to Application Example 21, wherein the deposition includes deposition by atomic layer deposition. [Application Example 24] 13. The method according to claim 12, wherein the organometallic compound has the formula (II): M a R b L c (II) and During the ceremony, M is a metal, each R is independently an EUV-labile ligand, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is independently a ligand, ion, or other moiety reactive with a counter reactant, and R and L together with M can optionally form a heterocyclyl group, or R and L together can optionally form a heterocyclyl group; a ≥ 1; b ≥ 1; and c ≥ 1, method. [Application Example 25] The method according to Application Example 24, wherein R is optionally substituted alkyl and M is tin. [Application Example 26] The method according to Application Example 24, wherein each L is independently H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy. [Application Example 27] The method according to Application Example 24, wherein the film formation further includes a counter reactant. [Application Example 28] The method according to Application Example 7, wherein the deposition further includes a reducing gas or acetylene. [Application Example 29] The method according to Application Example 28, wherein the reducing gas is hydrogen (H 2 ), amines (NH 3 ), or a trialkylamine. [Application Example 30] The method according to Application Example 7, After the film formation, patterning the patterned radiation-sensitive coating by exposing it to patterned radiation, thereby resulting in an exposed coating having radiation-exposed and radiation-unexposed areas; and developing the exposed film, thereby removing the radiation-exposed areas to produce a pattern in a positive resist film, or removing the radiation-unexposed areas to produce a pattern in a negative resist. The method further comprises: [Application Example 31] The method according to Application Example 30, wherein the patterning radiation exposure comprises extreme ultraviolet exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum environment. [Application Example 32] 32. The method of claim 31, wherein the developing comprises dry developing chemicals or wet developing chemicals. [Application Example 33] 34. The method according to claim 33, wherein the dry developing chemicals are selected from the group consisting of HCl, HBr, HI, HF, Cl in a plasma. 2 、Br 2 , BCl 3 , B.F. 3 , NF 3 , N.H. 3 , SOCl 2 ,SCIENCE FICTION 6 , C.F. 4 , CHF 3 , C.H. 2 F 2 , and / or CH 3 F, including the method. [Application Example 34] The method according to Application Example 33, wherein the wet development chemicals include a ketone, an ester, an alcohol, or a glycol ether. [Application Example 35] The method according to Application Example 34, wherein the wet development chemicals include 2-heptanone, cyclohexanone, acetone, γ-butyrolactone, n-butyl acetate, ethyl 3-ethoxypropionate, isopropyl alcohol (IPA), propylene glycol methyl ether (PGME), or propylene glycol methyl ether acetate (PGMEA), or a combination thereof. [Application Example 36] An apparatus for forming a resist film, comprising: a deposition module comprising a chamber for depositing a patterned radiation sensitive coating; a patterning module comprising a photolithography tool having a source of sub-300 nm wavelength radiation; a development module having a chamber for developing the resist film; a controller including one or more memory elements, one or more processors, and system control software coded with instructions including machine-readable instructions, the machine-readable instructions comprising: causing, in the deposition module, depositing a tantalum-based precursor including a patterned radiation-sensitive moiety on an upper surface of a semiconductor substrate to form the patterned radiation-sensitive coating as a resist coating; in the patterning module, directly patterning the resist film with patterning radiation exposure at sub-300 nm resolution, thereby causing the formation of an exposed film having radiation-exposed and radiation-unexposed regions; developing the exposed film in the developing module to remove either the radiation-exposed areas or the radiation-unexposed areas, causing a pattern in the resist film; A controller; An apparatus comprising: [Application Example 37] The apparatus of Application Example 36, wherein the patterning radiation-sensitive coating comprises an extreme ultraviolet (EUV)-sensitive coating. [Application Example 38] The apparatus of Application Example 37, wherein the source of the photolithography tool is a source of sub-30 nm wavelength radiation. [Application Example 39] 39. The apparatus of claim 38, wherein the machine-readable instructions include: The apparatus further includes instructions for causing, in the patterning module, directly patterning the resist film with EUV exposure at sub-30 nm resolution, thereby forming the exposed film having EUV-exposed regions and EUV-unexposed regions. [Example 40] 39. The apparatus of claim 39, wherein the machine-readable instructions include: The apparatus further comprising instructions for causing, in the developing module, developing the exposed film to remove the EUV-exposed areas or the EUV-unexposed areas to produce a pattern in the resist film. [Application Example 41] In the device according to any one of Aspects 37 to 40, the instructions including the machine-readable instructions are: the apparatus further comprising instructions for further depositing, in the deposition module, an organometallic compound in the optional presence of a reducing gas, acetylene, and / or a counter reactant, causing the tantalum-based precursor and the organometallic compound to be co-deposited, resulting in a mixed organometallic film having two or more different metals. [Application Example 42] In the device according to any one of Aspects 37 to 40, the instructions including the machine-readable instructions are: the apparatus further comprising instructions for causing, in the deposition module, further depositing an organometallic compound in the optional presence of a reducing gas, acetylene, and / or a counter reactant, wherein the tantalum-based precursor and the organometallic compound are deposited in alternating cycles to result in an organometallic-containing layer and a tantalum-containing layer disposed on top of the organometallic-containing layer. [Application Example 43] 1. A method comprising: providing a patterned radiation sensitive coating disposed on an upper surface of a semiconductor substrate, said coating comprising tantalum or tantalum and tin; and patterning said patterned radiation-sensitive coating by exposing it to patterning radiation, thereby providing an exposed coating having radiation-exposed areas and radiation-unexposed areas. A method comprising: [Example 44] The method according to Application Example 43, The method further comprising, after said patterning, developing said exposed film using wet chemistry. [Application Example 45] The method according to Application Example 43, The method further comprising, after said providing said patterned radiation sensitive coating, performing a post-apply bake at a temperature below 250°C or below 180°C. [Application Example 46] The method according to Application Example 43, The method further comprising performing a post-exposure bake after said patterning at a temperature below 250°C or below 180°C.

Claims

1. 1. A method for forming a coating, comprising: depositing a tantalum-based precursor on a surface of a substrate to provide a patterned radiation-sensitive coating; Including, the tantalum-based precursor comprises a patterned radiation-sensitive moiety; the patterning radiation-sensitive coating comprises an extreme ultraviolet (EUV)-sensitive coating; The tantalum-based precursor has formula (IA): () () b (_) and In formula (IA), R is =NR i or =CR i R ii and Each L is independently halogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or a divalent ligand bonded to Ta, said divalent ligand being -NR i -Ak-NR ii - and Each R i and R ii are independently H, optionally substituted linear alkyl, optionally substituted branched alkyl, or optionally substituted cycloalkyl; Ak is an optionally substituted alkylene or an optionally substituted alkenylene; b≧1; method.

2. 10. The method of claim 1, wherein the patterning radiation-sensitive moieties of the tantalum-based precursor comprise EUV-labile groups.

3. 3. The method of claim 1 or 2, wherein the patterned radiation sensitive coating comprises a tantalum nitride coating.

4. 3. The method of claim 1 or 2, wherein the patterned radiation-sensitive coating further comprises an organometallic compound, and the tantalum-based precursor and the organometallic compound can be deposited together.

5. 5. The method of claim 4, wherein the depositing further comprises adjusting the relative amounts of the tantalum-based precursor and the organometallic compound deposited in the film.

6. 6. The method of claim 5, wherein the adjusting comprises changing flow rates and / or deposition times of the tantalum-based precursor and the organometallic compound.

7. 5. The method of claim 4, wherein the deposition comprises: depositing the tantalum-based precursor and the organometallic compound in the presence of a reducing gas or acetylene, or in the absence of the reducing gas and the acetylene, thereby providing the patterned radiation-sensitive coating comprising a mixed organometallic coating having two or more different metals.

8. 8. The method of claim 7, wherein the organometallic compound comprises a tin-based precursor and the mixed organometallic coating comprises tantalum and tin.

9. 8. The method of claim 7, wherein the deposition comprises deposition by chemical vapor deposition at a temperature below 250°C.

10. 3. The method of claim 1 or 2, wherein the patterned radiation-sensitive coating further comprises an organometallic compound, and the tantalum-based precursor and the organometallic compound can be deposited sequentially in sequence.

11. 11. The method of claim 10, wherein the sequence includes depositing the tantalum-based precursor followed by or preceding the deposition of the organometallic compound.

12. 11. The method of claim 10, wherein the deposition further comprises adjusting the number or order of sequences of deposition of the tantalum-based precursor followed by or preceding deposition of the organometallic compound.

13. 11. The method of claim 10, The film formation is depositing the organometallic compound in a chamber in the presence or absence of a counter reactant, thereby providing an organometallic-containing layer; purging the chamber with a purge gas; depositing the tantalum-based precursor in the chamber, thereby providing a tantalum-containing layer disposed on an upper surface of the organometallic-containing layer; purging the chamber with another purge gas; and exposing the tantalum-containing layer to a reducing gas or acetylene; A method comprising:

14. 14. The method of claim 13, wherein the organometallic compound comprises a tin-based precursor and the organometallic-containing layer comprises tin.

15. 14. The method of claim 13, wherein the depositing comprises depositing by atomic layer deposition.

16. 5. The method of claim 4, wherein the organometallic compound has the formula (II): - a 2 b L c (A) and In formula (II), M is a metal, each R is independently an EUV-labile ligand, halogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is independently a ligand reactive with a counter reactant, an ion reactive with said counter reactant, or other moiety reactive with said counter reactant, and R and L together with M can optionally form a heterocyclyl group, or R and L together can optionally form a heterocyclyl group; a > 1; b > 1; and c > 1; method.

17. 17. The method of claim 16, wherein R is optionally substituted alkyl and M is tin.

18. 17. The method of claim 16, wherein each L is independently H, halogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy.

19. 17. The method of claim 16, wherein the deposition is performed in the presence of a counter reactant.

20. 10. The method of claim 1, wherein the deposition is performed in the presence of a reducing gas or acetylene.

21. 21. The method of claim 20, wherein the reducing gas is hydrogen (H 2 ), amine (NH 3 ), or a trialkylamine.

22. 10. The method of claim 1, After the film formation, patterning the patterned radiation-sensitive coating by exposing it to patterned radiation, thereby resulting in an exposed coating having radiation-exposed and radiation-unexposed areas; and developing the exposed film, thereby removing the radiation-exposed areas to produce a pattern in a positive resist film, or removing the radiation-unexposed areas to produce a pattern in a negative resist. The method further comprises:

23. 23. The method of claim 22, wherein the patterning radiation exposure comprises extreme ultraviolet exposure having a wavelength in the range of 10 nm to 20 nm in a vacuum environment.

24. 24. The method of claim 23, wherein the developing comprises dry or wet developing chemistry.

25. 25. The method of claim 24, wherein the dry development chemistry is HCl, HBr, HI, HF, Cl in a plasma. 2 ,Br 2 , BCl 3 , B.F. 3 , N.F. 3 , N.H. 3 , SOCl 2 , SF 6 , C.F. 4 , CHF 3 , C.H. 2 F 2 , and / or CH 3 A method comprising:

26. 25. The method of claim 24, wherein the wet development chemicals include a ketone, an ester, an alcohol, or a glycol ether.

27. 27. The method of claim 26, wherein the wet development chemicals include 2-heptanone, cyclohexanone, acetone, gamma-butyrolactone, n-butyl acetate, ethyl 3-ethoxypropionate, isopropyl alcohol (IPA), propylene glycol methyl ether (PGME), or propylene glycol methyl ether acetate (PGMEA), or combinations thereof.

Images