HALOGEN AND ALIPHATIC-CONTAINING ORGANOTIN PHOTORESISTS AND METHODS THEREOF - Patent application

Abstract

This disclosure is 1-4 Haloaliphatic group or C 1-4 The present invention relates to compositions formed using precursors containing aliphatic or vinyl groups (—CH═CH) and other unsaturated substituents, and methods for forming and using such compositions. In certain embodiments, the haloaliphatic group is 1-2 In other embodiments, the aliphatic group is a haloalkyl group, which provides a resist film with improved radiation absorptivity and / or minimal film shrinkage (e.g., upon radiation exposure and / or post-exposure bake). 1-2 Alkyl or vinyl groups and other unsaturated substituents, which can be dry deposited. In a non-limiting embodiment, the radiation can include extreme ultraviolet (EUV) radiation or deep ultraviolet (DUV) radiation.

Description

Incorporation by Reference

[0001] A PCT application is being filed contemporaneously herewith as a part of this application, and each application identified in that contemporaneously filed PCT application to which this application claims benefit or priority is hereby incorporated by reference in its entirety for all purposes. [Technical field]

[0002] This disclosure relates to 1-4 Haloaliphatic group or C 1-4 The present invention relates to compositions formed using precursors that contain aliphatic or vinyl groups (-CH=CH2) and other unsaturated substituents, and methods for forming and using such compositions. In certain embodiments, the haloaliphatic group is 1-2 In another embodiment, the aliphatic group is a haloalkyl group, which provides a resist film with improved radiation absorptivity and / or minimal film shrinkage (e.g., upon radiation exposure and / or post-exposure bake). 1-2 Alkyl or vinyl groups and other unsaturated substituents, which can be dry deposited. In a non-limiting embodiment, the radiation can include extreme ultraviolet (EUV) radiation or deep ultraviolet (DUV) radiation. [Background technology]

[0003] The background description provided herein is intended to provide a general overview of the present technology. Work by the currently named inventors within the scope of what is described in this Background section, as well as aspects of the description that may not otherwise be considered prior art at the time of filing, are not admitted, expressly or impliedly, as prior art against the present technology.

[0004] Patterning of thin films in semiconductor processing is often a critical step in the fabrication of semiconductors. Patterning involves lithography. In traditional photolithography, such as 193 nm photolithography, a pattern is printed by emitting photons from a photon source onto a mask and printing the pattern onto a light-sensitive photoresist, which triggers chemical reactions in the photoresist that, after development, remove certain portions of the photoresist to form the pattern.

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

[0006] Extreme ultraviolet (EUV) lithography can extend lithography techniques by moving to shorter imaging source wavelengths than can be achieved with traditional photolithography methods. EUV sources with wavelengths of about 10-20 nm, or 11-14 nm, for example 13.5 nm, can be used for state-of-the-art lithography tools, also called scanners. EUV radiation is strongly absorbed by a wide range of solid and fluid materials, including quartz, air, and water vapor, and therefore operates in a vacuum. Summary of the Invention

[0007] This disclosure relates to 1-4 Haloaliphatic or C 1-4 It relates to the use of precursors having aliphatic or C2 (vinyl) and other unsaturated substituents. In certain embodiments, the haloaliphatic groups provide haloalkyl groups in the deposited film, where the halogen atoms can provide enhanced radiation absorptivity and reactivity (compared to the hydrogen atoms present in non-halogenated alkyl groups).

[0008] Such haloaliphatic and aliphatic groups also include, for example, 1-2 Haloalkyl group or C 1-2 Like alkyl groups, they can be characterized as relatively small. The use of such groups can lead to higher film packing, which can be characterized by increased film density (compared to the use of precursors with bulky alkyl groups, such as branched C4 tert-butyl groups). In some embodiments, such small groups can facilitate all dry processes (e.g., dry deposition, dry development, and dry etching) due to the high volatility of the precursors and etching by-products. In particular, the use of dry processes can eliminate the need for the requirement that the resist film be soluble in solvent-based development processes, etc.

[0009] Furthermore, the use of such haloaliphatic and aliphatic groups can reduce film shrinkage upon radiation exposure or post-exposure bake. For example, upon exposure to radiation and / or heat, such haloaliphatic or aliphatic groups generally cleave or react, thereby increasing the contrast in material properties between exposed and unexposed regions. Cleavage of such groups can lead to voids in the film, which can result in radiation and bake-induced shrinkage effects. By using relatively small haloaliphatic and aliphatic groups, such shrinkage effects can be minimized. Thus, the present disclosure encompasses the use of precursors having relatively small haloaliphatic and aliphatic groups, thereby providing films with improved radiation sensitivity, improved patterning quality (e.g., improved line width roughness (LWR) and / or line edge roughness (LER)), increased film density, reduced dose-to-size (DtS), and / or minimized film shrinkage upon exposure to radiation, heat, or other post-patterning processes (e.g., etching).

[0010] In a first aspect, the present disclosure encompasses patterning radiation-sensitive films comprising organometallic-oxo materials. In some embodiments, the materials are composed of metal, oxygen, and C. 1-4Haloaliphatic or C 1-4 In another embodiment, C 1-4 Aliphatic is C 1-2 Alkyl, C 2-4 Alkenyl, and C 2-4 In yet another embodiment, C is selected from the group consisting of alkynyl, 1-4 Haloaliphatic is C 1-4 Haloalkyl, C 2-4 Haloalkenyl, and C 2-4 In some embodiments, the material is selected from a haloalkynyl. 1-2 It is an alkylmetal-oxo material. In certain embodiments, the metal is tin (Sn).

[0011] In some embodiments, C 1-4 Haloalkyl includes halo-substituted methyl containing one, two, or three halo substituents (e.g., fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, bromofluoromethyl, chlorofluoromethyl, fluoroiodomethyl, etc.). 1-2 Haloalkyl is -CX y H 3-y wherein y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I).

[0012] In some embodiments, C 1-4 Haloalkyl includes β-halo substituted ethyl containing one, two, or three halo substituents (e.g., 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2-dichloroethyl, 2,2-dibromoethyl, 2,2-diiodoethyl, 2,2-fluoroiodoethyl, etc.). In other embodiments, C 1-2 Haloalkyl is -CHCX y H 3-ywherein y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I). 1-2 Haloalkyl is -CX z H 2-z CX y H 3-y wherein z is 0, 1, or 2; y is 0, 1, 2, or 3; each X is independently halo (F, Cl, Br, or I); and at least one of z or y is not 0.

[0013] In some embodiments, C 1-4 The haloaliphatic includes one or more fluoro or iodine substituents. Without wishing to be limited by mechanism, films having such fluoro and iodine substituents can be processed by dry processes including dry deposition, dry development, and / or dry etching. In certain embodiments, films are deposited by using volatile precursors having such fluoro and iodine substituents, thereby allowing dry deposition of the precursor in the gas phase. Optionally, such films can be dry developed, for example, to provide a negative resist, where the radiation-exposed regions provide non-volatile materials and the radiation-unexposed regions provide volatile by-products when exposed to dry development chemistries (e.g., vapor-based etchant chemistries as described herein). In this manner, etchants in the gas phase can be used to react with the unexposed film to provide volatile by-products, which can also be removed in vapor form. Within the radiation-exposed regions, such haloaliphatic groups can be present in any useful form. In one example, a haloaliphatic group can form a bridge between metal atoms (e.g., M-Ak-M, where Ak is a haloalkylene group and M is a metal such as tin.) In another example, a halo atom can be removed from a haloaliphatic group (e.g., by exposure to radiation) and the halo atom can be incorporated into the film.

[0014] In another embodiment, C 1-4The aliphatic groups are selected from methyl, ethyl, vinyl, ethynyl, propenyl, and propargyl. Without wishing to be limited by mechanism, unsaturated aliphatic groups (e.g., C 2-4 Alkenyl or C 2-4 The alkynyl) can be present in the film in any useful manner. In certain embodiments, the unsaturated groups can undergo photoinduced polymerization (e.g., by exposure to radiation), thereby forming interligand bonds between the unsaturated groups. In other embodiments, the unsaturated groups can form aliphatic bridges between metal atoms (e.g., (e.g., M-Ak-M, where Ak is an alkylene group and M is a metal such as tin).

[0015] In another embodiment, C 1-2 Alkyl includes methyl or ethyl. In yet other embodiments, C 2-4 Alkenyl includes ethenyl, propenyl (e.g., 1-propenyl or 2-propenyl), or butenyl (e.g., 1-butenyl, 2-butenyl, or 3-butenyl). 2-4 Alkynyl includes ethynyl, propynyl (eg, 1-propynyl or 2-propynyl), or butynyl (eg, 1-butynyl, 2-butynyl, or 3-butynyl).

[0016] In some embodiments, the membrane further comprises a vertical gradient extending from the upper surface of the membrane to the lower portion of the membrane. In certain embodiments, the upper portion of the membrane (e.g., near the upper surface of the membrane) has a C 3-4 In other embodiments, the lower portion (e.g., near the bottom surface of the substrate or film) comprises a C 1-4 Haloaliphatic groups, C 1-2 Alkyl group, C 2-4 Alkenyl group, or C 2-4 Contains alkynyl groups.

[0017] In a second aspect, the present disclosure provides a method of using a resist comprising depositing a metal-containing precursor and an optional ligand-containing precursor on a surface of a substrate to provide a resist film, the resist film comprising a metal, oxygen, and C. 1-4Haloaliphatic or C 1-4 The present invention includes a method of comprising comprising:

[0018] In some embodiments, C 1-4 Haloaliphatic is C 1-4 Haloalkyl, C 2-4 Haloalkenyl, and C 2-4 In another embodiment, C is selected from haloalkynyl. 1-4 Aliphatic is C 1-2 Alkyl, C 2-4 Alkenyl, and C 2-4 alkynyl.

[0019] In some embodiments, the depositing comprises providing a metal-containing precursor, hi certain embodiments, the metal-containing precursor is an organometallic precursor.

[0020] In some embodiments, the metal-containing precursor has formula (I): M a R b L c (I)

[0023] Each M is independently a metal (e.g., tin (Sn)) and each R is independently an optionally substituted C 1-4 Haloaliphatic or optionally substituted C 1-4 aliphatic, and each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety that reacts with the reverse reactant and / or the ligand-containing precursor, where a > 1, b > 1, and c > 1. In certain embodiments, the reverse reactant is water vapor.

[0021] In other embodiments, the metal-containing precursor has the formula (Ia): SnR b L 3-b (Ia)

[0023] Each R is independently an optionally substituted C1-4 Haloaliphatic or optionally substituted C 1-4 aliphatic, each L is independently halo, optionally substituted amino, optionally substituted alkoxy, or a ligand that reacts with a reverse reactant and / or a ligand-containing precursor, and b is 1 or 2. In certain embodiments, the reverse reactant is water vapor.

[0022] In some embodiments, the depositing comprises providing a ligand-containing precursor, which can be provided simultaneously or sequentially with the metal-containing precursor. In one embodiment, the ligand-containing precursor introduces additional L groups onto metal centers M present in the metal-containing precursor or in the resist film.

[0023] In some embodiments, the metal-containing precursor has formula (III): M a L c (III)

[0023] Each M is independently a metal, each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety reactive with a reverse reactant and / or a ligand-containing precursor, a>1, and c>1.

[0024] In other embodiments, the metal-containing precursor has the formula (IIIa): SnL2(IIIa)

[0023] Each L is independently halo, optionally substituted amino, optionally substituted alkoxy, or a ligand that reacts with a reverse reactant and / or a ligand-containing precursor.

[0025] In some embodiments, the depositing comprises providing a ligand-containing precursor, the ligand-containing precursor introducing additional L and R groups onto a metal center M present in the metal-containing precursor or in the resist film. In certain embodiments, the metal-containing precursor comprises a structure having formula (III) and the ligand-containing precursor comprises a structure having formula (IV): R f L g (IV)

[0023] Each R is independently an optionally substituted C 1-4 Haloaliphatic or optionally substituted C 1-4 aliphatic, each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety reactive with a reverse reactant and / or a metal-containing precursor, f≧1, and g≧1.

[0026] In other embodiments, the ligand-containing precursor has formula (IVa): RL(IVa)

[0023] Each R is independently an optionally substituted C 1-4 Haloaliphatic or optionally substituted C 1-4 aliphatic, and each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety that reacts with a reverse reactant and / or a metal-containing precursor. In certain embodiments, L is halo. In other embodiments, L is alkoxy.

[0027] In other embodiments, a metal-containing precursor comprising formula (III) is reacted with a ligand-containing precursor comprising formula (IV) to provide a precursor comprising a structure having formula (I). In yet other embodiments, the depositing comprises simultaneously or sequentially providing a metal-containing precursor comprising formula (III) and a ligand-containing precursor comprising formula (IV).

[0028] In some embodiments, the depositing step includes providing a metal-containing precursor and an optional ligand-containing precursor in vapor form. In other embodiments, the depositing step further includes providing a reverse reactant. Non-limiting reverse reactants can include oxygen-containing reverse reactants or chalcogenide-containing precursors. In certain embodiments, the reverse reactant is water vapor.

[0029] In other embodiments, the depositing of the metal-containing precursor and the ligand-containing precursor is performed in succession or alternating cycles. In some embodiments, the depositing includes delivering the metal-containing precursor together with an optional reverse reactant to a chamber configured to provide a substrate, purging the chamber to remove the metal-containing precursor and / or the optional reverse reactant, and delivering the ligand-containing precursor to the chamber, thereby forming a resist film. In certain embodiments, the delivering of the metal-containing precursor, the purging, and the delivering of the ligand-containing precursor can be performed one or more times.

[0030] In yet other embodiments, the depositing further comprises a second metal-containing precursor that forms an upper portion of the film, thereby providing a gradient film. In some embodiments, the second metal-containing precursor is a C that is deposited as the upper portion of the film. 3-4 In another embodiment, the first metal-containing precursor comprises a C 1-4 Haloaliphatic groups, C 1-2 Alkyl group, C 2-4 Alkenyl group, or C 2-4 A first metal-containing precursor, which includes an alkynyl group, is deposited as the lower portion of the film.

[0031] In a further embodiment, the method may further include patterning the resist film by exposing it to patterned radiation, thereby providing an exposed film having radiation exposed and non-radiation exposed areas, and developing the exposed film, thereby removing the radiation exposed areas to provide a pattern in a positive tone resist film, or removing the non-radiation exposed areas to provide a pattern in a negative tone resist.

[0032] In some embodiments, the patterning comprises EUV exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum atmosphere.

[0033] In other embodiments, the developing comprises wet developing or dry developing. Non-limiting wet developing may include water, acid, base, ketone, ester, alcohol, ether, or combinations thereof. In further embodiments, the wet developing further comprises one or more surfactants. In other embodiments, the dry developing comprises a gaseous acid. In some embodiments, the developing comprises removing radiation-exposed areas to provide a pattern in a positive resist film. In other embodiments, the developing comprises removing radiation-unexposed areas to provide a pattern in a negative resist.

[0034] In a third aspect, the present disclosure encompasses an apparatus for forming a resist film, the apparatus including a deposition module and a controller including one or more memory devices, one or more processors, and system control software encoded with instructions including machine-readable instructions. In certain embodiments, the deposition module includes a chamber for depositing a resist film (e.g., a patterning radiation sensitive film such as an EUV sensitive film), and the chamber can be configured to accommodate a semiconductor substrate.

[0035] In one embodiment, the instructions include machine-readable instructions for depositing (e.g., in a deposition module) a metal-containing precursor and an optional ligand-containing precursor on an upper surface of a semiconductor substrate to form a resist film, the resist film comprising a metal, oxygen, and C. 1-4 Haloaliphatic or C 1-4 In certain embodiments, C 1-4 Aliphatic is C 1-2 Alkyl, C 2-4 Alkenyl, and C 2-4 alkynyl.

[0036] In some embodiments, the apparatus further includes a patterning module. In other embodiments, the patterning module includes a photolithography tool having a radiation source with a wavelength of less than 300 nm (e.g., the source can be a radiation source with a wavelength of less than 30 nm). In some embodiments, the instructions include machine-readable instructions for patterning (e.g., in the patterning module) the resist film directly by patterning radiation exposure (e.g., by EUV exposure) at a resolution of less than 300 nm (e.g., or with radiation with a wavelength of less than 30 nm), thereby forming an exposed film having radiation exposed regions and radiation unexposed regions. In other embodiments, the exposed film has EUV exposed regions and EUV unexposed regions.

[0037] In some embodiments, the apparatus further includes a developing module. In other embodiments, the developing module includes a chamber for developing the resist film. In further embodiments, the instructions include machine-readable instructions for causing development of the exposed film (e.g., in the developing module) to remove radiation exposed or non-radiation exposed areas to provide a pattern in the resist film. In certain embodiments, the machine-readable instructions include instructions for removing EUV exposed or non-EUV exposed areas.

[0038] In some embodiments, the resist film comprises a gradient film. In certain embodiments, the gradient film can be characterized by a vertical gradient that extends from the top surface of the film to a lower portion of the film. In one embodiment, the vertical gradient is a C that increases from the top surface of the film toward the substrate. 1-4 Haloaliphatic groups, C 1-2 Alkyl group, C 2-4 Alkenyl group, or C 2-4 In this case, a higher density or more of the EUV absorbing composition is provided in the lower portion of the film. In some embodiments, the vertical gradient is 3-8 The upper portion of the membrane bearing alkyl groups (e.g., metal, oxy, and C 3-8 (organometallic-oxo materials containing alkyl groups) and C 1-4 Haloaliphatic groups, C 1-2 Alkyl group, C 2-4 Alkenyl group, or C 2-4 The lower portion of the membrane having alkynyl groups (e.g., metal, oxy, and C 1-4 Haloaliphatic groups, C 1-2 Alkyl group, C 2-4 Alkenyl group, or C 2-4 In another embodiment, the vertical gradient comprises C 3-8 The upper portion of the membrane has alkyl groups (e.g., organometallic-oxo materials containing metal, oxy, and isopropyl groups) and C 1-4 Haloaliphatic groups, C 1-2 Alkyl group, C 2-4 Alkenyl group, or C 2-4 and a lower portion of the film having alkynyl groups (e.g., metal, oxy, and organometallic-oxo materials containing methyl or ethyl groups). In yet other embodiments, the vertical gradient is characterized by a vertical change in EUV absorbance. In some cases, an increase in EUV absorbance along the depth (e.g., from the top surface of the film toward the substrate) may correspond to an increase in metal content, halogen content, or density along the same depth through the film layer.

[0039] In any embodiment herein, the patterned radiation sensitive film (eg, resist film) comprises an extreme ultraviolet (EUV) sensitive film, a deep ultraviolet (DUV) sensitive film, a photoresist film, or a photopatternable film.

[0040] In any of the embodiments herein, the patterned radiation-sensitive film (eg, resist film) comprises an organometallic or organometallic oxide material.

[0041] In any of the embodiments herein, the patterned radiation-sensitive film (eg, resist film) comprises an organotinoxy, an organotin oxide, or an organotin oxide hydroxide.

[0042] In any of the embodiments herein, the patterned radiation sensitive film (e.g., resist film) is a film containing metal, oxygen, and C. 1-4 Haloaliphatic or C 1-4 In some embodiments, the metal in the film comprises tin (Sn). In other embodiments, the C in the film comprises 1-2 Haloaliphatic includes halo-substituted methyl containing 1, 2, or 3 halo substituents, or β-halo-substituted ethyl containing 1, 2, or 3 halo substituents. In yet another embodiment, the membrane has a metal-oxygen bond and a metal-C 1-4 Haloalkyl bonds (e.g., metal-C 1-2 In some embodiments, the membrane comprises a haloalkylmetal-oxo material that includes a network of metal-oxygen bonds and metal-C 1-2 Alkyl bond or metal-C 2-4 Alkenyl bond or metal-C 2-4 In another embodiment, the C in the film includes an alkylmetal-oxo material that includes a network of alkynyl bonds. 1-4 Aliphatic includes methyl, ethyl, vinyl, ethynyl, propenyl, or propargyl.

[0043] In any of the embodiments herein, the dose-to-gel of the patterned radiation sensitive film (e.g., resist film) is determined based on the metal, oxygen, and C. 1-4Aliphatic (e.g., C 1-4 Alkyl, C 2-4 Alkyl, or C 3-4 The dose versus gel of a non-halogenated film containing haloaliphatic groups is lower than that of a non-halogenated film containing haloaliphatic groups (e.g., any of those described herein containing haloaliphatic groups). In certain embodiments, the resist film is a halogenated film compared to a non-halogenated film, the non-halogenated film containing the same amount and type of metal and oxygen atoms as a halogenated film (e.g., any of those described herein containing haloaliphatic groups), except that the aliphatic groups present in the non-halogenated film are present as haloaliphatic groups in the halogenated film. In other embodiments, the resist film is a first non-halogenated film compared to a second non-halogenated film, the first non-halogenated film containing the same amount and type of metal and oxygen atoms as the second non-halogenated film, except that the aliphatic groups present in the first film have fewer carbon atoms than the aliphatic groups in the second film.

[0044] In any of the embodiments herein, the patterned radiation-sensitive film (e.g., resist film) comprises a dense film. In other embodiments, the film has a density of about 1.6 to 4.5 g / cm. 3 has a density of

[0045] In any embodiment herein, the patterned radiation-sensitive film (eg, resist film) has a thickness of about 5 to 50 nm, for example, about 15 to 25 nm.

[0046] In any embodiment herein, each R is independently an optionally substituted C 1-4 Haloaliphatic or optionally substituted C 1-4 It is aliphatic. Non-limiting C 1-4 Haloaliphatic includes C 1-4 Haloalkyl, optionally substituted C 2-4 Haloalkenyl, and optionally substituted C 2-4 Non-limiting examples of C include haloalkynyl. 1-4 Aliphatic groups include optionally substituted C 1-2 Alkyl, optionally substituted C 2-4 Alkenyl, and optionally substituted C 2-4 Examples include alkynyl.

[0047] In any embodiment herein, each L is independently an optionally substituted alkoxy. Non-limiting alkoxy includes: 1-5 or C 1-4 Examples of such radicals include alkoxy.

[0048] In any embodiment herein, each L is independently an optionally substituted amino. Non-limiting amino includes: 1-5 or C 1-4 Dialkylamino is an example.

[0049] In any embodiment herein (e.g., of Formula (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), (Va), (VI), (VII), (VIII), (IX), (X), (XI), or other formulas described herein), each L is independently halo, optionally substituted amino, optionally substituted alkoxy, or a ligand that reacts with the reverse reactant and / or the ligand-containing precursor and / or the metal-containing precursor.

[0050] In any of the embodiments herein, the metal-containing precursor comprises a structure having formula (I), (Ia), (III), (IIIa), (V), (Va), (VI), (VII), (VIII), (IX), (X), or (XI) as described herein.

[0051] In any of the embodiments herein, the ligand-containing precursor comprises a structure having formula (II), (IIa), (IV), or (IVa) as described herein.

[0052] In some embodiments herein, a single metal-containing precursor is used with one or more ligand-containing precursors, while in other embodiments, two, three, four, or more different metal-containing precursors are used within one or more ligand-containing precursors.

[0053] In some embodiments herein, a single metal-containing precursor is used with a single ligand-containing precursor. In other embodiments, a single metal-containing precursor is used with two, three, four, or more different ligand-containing precursors. In yet other embodiments, two or more different metal-containing precursors are used with two or more different ligand-containing precursors.

[0054] In any embodiment herein, the depositing includes providing a metal-containing precursor and / or a ligand-containing precursor in vapor form. In other embodiments, the depositing includes providing a metal-containing precursor, a ligand-containing precursor, and / or a back reactant in vapor form. Non-limiting deposition processes include chemical vapor deposition (CVD), as well as atomic layer deposition (ALD), molecular layer deposition (MLD), and plasma-enhanced forms thereof.

[0055] In any embodiment herein, the depositing further comprises providing a reverse reactant. Non-limiting reverse reactants include oxygen-containing or chalcogenide-containing precursors, as well as any of those described herein (e.g., oxygen-containing reverse reactants including oxygen (O2), ozone (O3), water, peroxides, 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). Additional details are as follows:

[0056] definition "Aliphatic" means a group consisting of at least 1 carbon atom and at least 50 carbon atoms (C 1-50 ), e.g., 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10), which includes alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic versions thereof, as well as straight and branched chain arrangements, and all stereoisomers and positional isomers. Such hydrocarbons may be unsubstituted or substituted with one or more groups, such as those described herein for alkyl groups.

[0057] "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 can be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more of the substituents described herein for alkyl. Non-limiting unsubstituted alkenyl groups include C 2-8 Alkenyl, C 2-6 Alkenyl, C 2-5 Alkenyl, C 2-4 Alkenyl, or C 2-3 Exemplary non-limiting alkenyl groups include vinyl or ethenyl (-CH=CH2), 1-propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (e.g., -CH2CH2CH=CH2), 2-butenylidene (e.g., =CH-CH=CHCH3), and the like.

[0058] "Alkenylene" means a polyvalent (e.g., divalent) form of an alkenyl group, which is an optionally substituted C alkyl group having one or more double bonds. 2-24 An alkenylene group is a cyclic (e.g., C 3-24The alkenylene group can be cyclic, cycloalkenyl, or acyclic. The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substituents described herein for alkyl. Exemplary non-limiting alkenylene groups include -CH=CH- or -CH=CHCH2-.

[0059] "Alkoxy" refers to -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. An alkoxy group can be substituted or unsubstituted. For example, an alkoxy group can be substituted with one or more of the substituents 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 of the alkyl group include alkoxy groups.

[0060] 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 or nPr), isopropyl (i-Pr or iPr), cyclopropyl, n-butyl (n-Bu or nBu), isobutyl (i-Bu or iBu), s-butyl (s-Bu or sBu), t-butyl (t-Bu or tBu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. An alkyl group can be a cyclic (e.g., C 3-24The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can include a haloalkyl, where the alkyl group is substituted with one or more halo groups as described herein. In another example, the alkyl group can be substituted with 1, 2, 3, or, in the case of an alkyl group of 2 or more carbons, 4 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 , R N1 and R N2 Each of is independently 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, phosphorus, sulfur, or halo, unless otherwise specified), (12) heterocyclyloxy (e.g., -O-Het, where Het is a heterocyclyl as described herein), (13) heterocyclyloyl (e.g., -C(O)-Het, where Het is a 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 , R A (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c) (C 4-18 Aryl)C 1-6 (19) -C(O)NR B R C , R B and R C each of which is independently (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 , 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); 2-6 alkynyl (e.g., optionally substituted alkyl having one or more triple bonds); (f) C 4-18 Aryl, (g) (C4-18 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, there are no two groups attached to the nitrogen atom via a carbonyl group. The alkyl group can 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 selected from the group consisting of C 1-2 , 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 2-24 It is an alkyl group.

[0061] "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 can be branched or unbranched. The alkylene group can also be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more of the substituents described herein for alkyl.

[0062] "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 of the substituents described herein for alkyl. Non-limiting unsubstituted alkynyl groups include C 2-8 Alkynyl, C 2-6 Alkynyl, C 2-5 Alkynyl, C 2-4 Alkynyl, or C 2-3 Exemplary non-limiting alkynyl groups include ethynyl (-C≡CH), 1-propynyl (-C≡CCH), 2-propynyl or propargyl (-CHC≡CH), 1-butynyl (-C≡CCHCH), 2-butynyl (-CHC≡CCH), 3-butynyl (-CHCHC≡CH), and the like.

[0063] "Alkynylene" means a polyvalent (e.g., divalent) form of an alkynyl group, which is an optionally substituted C alkyl group having one or more triple bonds. 2-24 It is an alkyl group. An alkynylene group can be cyclic or non-cyclic. An alkynylene group can be substituted or unsubstituted. For example, an alkynylene group can be substituted with one or more of the substituents described herein for alkyl. Exemplary non-limiting alkynylene groups include -C≡C- or -C≡CCH2-.

[0064] "Amino" means -NR N1 R N2 means R N1 and R N2is independently H, optionally substituted alkyl, or optionally substituted aryl, or R N1 and R N2 together with the nitrogen atom to which each is attached form a heterocyclyl group, as defined herein.

[0065] "Aminoalkyl" means an alkyl group, as defined herein, substituted by an amino group, as defined herein.

[0066] "Aminoaryl" means an aryl group, as defined herein, substituted by an amino group, as defined herein.

[0067] "Aryl" refers to fused benzo-C groups, such as, but not limited to, indanyl, tetrahydronaphthyl, and fluorenyl. 4-8 It refers to groups that contain any carbon-based aromatic group, including phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, and the like, including cycloalkyl radicals (e.g., as defined herein). The term aryl also includes heteroaryl, which is defined as a group that contains an aromatic group with 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, which is also included in the term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with 1, 2, 3, 4, or 5 substituents, such as those described herein for alkyl.

[0068] "Carbonyl" refers to the group -C(O)-, which also can be represented as >C=O.

[0069] "Cycloalkyl," unless otherwise specified, means a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group of three to eight 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.

[0070] "Dicarbonyl" means any moiety or compound that contains two carbonyl groups, as defined herein. Non-limiting dicarbonyl moieties include 1,2-dicarbonyl (e.g., R C1 -C(O)-C(O)R C2 , R C1 and R C2 each of which is independently an optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group), 1,3-dicarbonyl (e.g., R C1 -C(O)-C(R 1a R 2a )-C(O)R C2 , R C1 and R C2 each is independently an optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group; R 1a and R 2a each of which is independently H or an optional substituent provided for alkyl as defined herein), and 1,4-dicarbonyl (e.g., R C1 -C(O)-C(R 1a R 2a )-C(R 3a R 4a )-C(O)R C2 , R C1 and R C2 each is independently an optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group; R 1a , R 2a , R 3a , and R4a Each of is independently H, or an optional substituent provided for alkyl as defined herein.

[0071] "Halo" means F, Cl, Br, or I.

[0072] "Haloaliphatic" means an aliphatic group, as defined herein, that is substituted with one or more halo.

[0073] "Haloalkenyl" means an alkenyl group, as defined herein, substituted with one or more halo.

[0074] "Haloalkynyl" means an alkynyl group, as defined herein, substituted with one or more halo.

[0075] "Haloalkyl" means an alkyl group, as defined herein, that is substituted with one or more halo. Non-limiting unsubstituted haloalkyl groups include, but are not limited to, C 1-2 Haloalkyl, C 1-3 Haloalkyl, C 1-4 Haloalkyl, C 1-5 Haloalkyl, C 1-6 Haloalkyl, C 2-3 Haloalkyl, C 2-4 Haloalkyl, C 2-5 Haloalkyl, C 2-6 Haloalkyl, or C 3-6 Other non-limiting haloalkyl groups include -CX y H 3-y , y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I);-CX z H 2-z CX y H 3-y , z is 0, 1, or 2, y is 0, 1, 2, or 3, each X is independently halo (F, Cl, Br, or I), and at least one of z or y is not 0; y H 3-y, y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I);-CX z1 H 2-z1 CX z2 H 2-z2 CX y H 3-y each of z1 and z2 is independently 0, 1, or 2, y is 0, 1, 2, or 3, each X is independently halo (F, Cl, Br, or I), and at least one of z1, z2, or y is not 0; and -CX z H 1-z [CX y1 H 3-y1 ][CX y2 H 3-y2 ], z is 0 or 1, each of y1 and y2 is independently 0, 1, 2, or 3, each X is independently halo (F, Cl, Br, or I), and at least one of z, y1, or y2 is not 0.

[0076] "Haloalkylene" means an alkylene group, as defined herein, that is substituted with one or more halo.

[0077] "Heterocyclyl" means, unless otherwise specified, a 3-, 4-, 5-, 6-, or 7-membered ring (e.g., 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, phosphorus, sulfur, selenium, or halo). The 3-membered ring has 0-1 double bonds, the 4- and 5-membered rings have 0-2 double bonds, and the 6- and 7-membered rings have 0-3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups, in which any of the above heterocycles are 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 heterocycle such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, and the like. Heterocycles include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxanyl, benzodioxoc ...thiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benz zodioxocinyl, 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, benzoxathiazepinyl, 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, cytosinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diaziridinyl, dibenzoisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzooxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydropyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindol ... xanyl, dioxazinyl, dioxinyl, dioxiranyl, dioxenyl, dioxinyl, 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, in dolyl (e.g., 1H-indolyl or 3H-indolyl), isathinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazolyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidinyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthyridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl, naphthyridinyl,Octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanoyl, oxetanyl, oxetyl, oxenyl, oxindolyl, oxiranyl, oxobenzisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzo) zothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, 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, pyrrolidizinyl, pyrrolyl (e.g., For example, 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (for example, 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenadinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothio Phenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinediyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thiethyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl,Examples of heterocyclyl groups include thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, urisyl, uridinyl, xanthenyl, xanthinyl, xanthionyl, and the like, as well as modified forms thereof (e.g., containing one or more oxo and / or amino), 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.

[0078] "Hydroxyl" means --OH.

[0079] "Imino" means -NR-, where R can be H or optionally substituted alkyl.

[0080] "Oxo" means the group ═O.

[0081] "Oxy" means --O--.

[0082] As used herein, the term "about" means ±10% of the recited value. As used herein, the term modifies a recited value, a range of values, or one or more of the endpoints of a range.

[0083] As used herein, the terms "top," "bottom," "upper," "lower," "above," and "below" are used to provide relative relationships between structures. Use of these terms does not indicate or require that a particular structure must be located in a particular location within the apparatus.

[0084] Other features and advantages of the invention will become apparent from the following description and from the claims. [Brief description of the drawings]

[0085] [Figure 1A]FIG. 1A is a schematic diagram of a resist film formed by using a non-limiting metal-containing precursor (I-1). [Figure 1B] FIG. 1B is a schematic diagram of additional non-limiting metal-containing precursors: (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), (I-8), and (I-9).

[0086] [Figure 2A] FIG. 2A is a schematic diagram of a non-limiting metal-containing precursor (IA) reacted with a non-limiting ligand-containing precursor (II-A). [Figure 2B] FIG. 2B is a schematic diagram of another non-limiting metal-containing precursor (III-A) reacted with another non-limiting ligand-containing precursor (IV-A).

[0087] [Figure 3A] 3A is a schematic diagram of a non-limiting method using a resist film. A schematic diagram of a first non-limiting method 300 is shown, which includes depositing 301 a metal-containing precursor 30 together with an optional ligand-containing precursor 32. [Figure 3B] 3B is a flow diagram of a non-limiting method using a resist film. A flow diagram of another non-limiting method 350 is shown.

[0088] [Figure 4] FIG. 4 is a schematic diagram of one embodiment of a process station 400 for dry development.

[0089] [Diagram 5] FIG. 5 is a schematic diagram of one embodiment of a multi-station processing tool 500 .

[0090] [Figure 6] FIG. 6 is a schematic diagram of one embodiment of an inductively coupled plasma device 600 .

[0091] [Figure 7]FIG. 7 is a schematic diagram of one embodiment of a semiconductor process cluster tool architecture 700. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0092] The present disclosure generally relates to the field of semiconductor processing. In particular, the present disclosure is directed to using metal-containing precursors having haloaliphatic aliphatic groups, thereby providing organometallic films having such groups. Alternatively, metal-containing precursors can be used in combination with ligand-containing precursors, which can be used to introduce (halo)aliphatic groups onto the metal centers provided by the metal-containing precursors. As used herein, "(halo)aliphatic" is used to refer to both haloaliphatic and aliphatic groups. In some embodiments, the haloaliphatic group is a C 1-2 Haloalkyl, C 1-4 Haloalkyl, C 2-4 Haloalkenyl, or C 2-4 In other embodiments, the aliphatic group is C 1-2 Alkyl, C 2-4 Alkenyl, or C 2-4 It is alkynyl.

[0093] Reference will be made in detail herein to certain embodiments of the present disclosure. Examples of certain embodiments are illustrated in the accompanying drawings. Although the present disclosure will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the present disclosure to such specific embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents that 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 so as not to unnecessarily obscure the present disclosure.

[0094] EUV lithography utilizes an EUV resist that is patterned to form a mask for use in etching the underlying layer. The EUV resist may be a polymer-based chemically amplified resist (CAR) obtained by a liquid-based spin-on technique. An alternative to CAR is a directly photopatternable metal oxide-containing film, such as those available from Inpria Corp. (Corvallis, Oregon) and described in, for example, US Patent Application Publication No. 2017 / 0102612, US Patent Application Publication No. 2016 / 0216606, and US Patent Application Publication No. 2016 / 0116839, which are incorporated herein by reference at least for their disclosure of photopatternable metal oxide-containing films. Such films may be provided by spin-on techniques or dry vapor deposition. Metal oxide-containing films can be patterned directly (i.e., without the use of a separate photoresist) by EUV exposure in a vacuum atmosphere providing patterning resolution of less than 30 nm, as described, for example, in U.S. Pat. No. 9,996,004, issued June 12, 2018, and entitled EUV PHOTOPATTERNING OF VAPOR-DEPOSITED METAL OXIDE-CONTAINING HARDMASKS, and / or International Application No. PCT / US19 / 31618, entitled METHODS FOR MAKING EUV PATTERNABLE HARD MASKS, filed May 9, 2019, and published as International Publication No. WO2019 / 217749, the disclosures above relating at least to the composition, deposition, and patterning of direct photopatternable metal oxide films to form EUV resist masks, are incorporated herein by reference. Generally, patterning involves exposing an EUV resist to EUV radiation to form a photopattern in the resist, followed by development to remove portions of the resist according to the photopattern to form a mask.

[0095] Direct photopatternable EUV or DUV resists may be composed of or include metals and / or metal oxides mixed within an organic component. Metals / metal oxides are very promising in that they can enhance EUV or DUV photon adsorption, generate secondary electrons, and / or exhibit increased etch selectivity to the underlying film stack and device layers. To date, these resists have been developed using a wet (solvent) approach, which requires the wafer to be moved to a track where it is exposed to a developing solvent, dried, and then baked. This wet development step not only limits productivity, but can also lead to line collapse due to surface tension effects during evaporation of the solvent between fine features.

[0096] In general, by controlling the resist chemistry and / or the solubility or reactivity of the developer, the resist can be used as a positive or negative resist. It would be beneficial to have an EUV or DUV resist that can function as either a negative or positive resist.

[0097] Resist film and method thereof The present disclosure relates to organometallic resist films and methods thereof. In certain embodiments, the films include halogen-containing organometallic materials. Such materials can provide compact or dense films, which improve radiation absorption and limit bake and radiation shrinkage. Dense films can be achieved by using precursors with relatively small radiation cleavable groups. Such groups include, for example, C 1-2 (halo)aliphatic groups. Larger groups (e.g., C 3-12 A smaller C compared to the cleavage of the aliphatic group 1-2Cleavage and release of the (halo)aliphatic group results in smaller voids (where the group was present) upon exposure. Such voids may contribute to film shrinkage when the exposed film is further processed (e.g., by post-exposure, post-exposure etching, or other processes). By minimizing the size of the voids, film shrinkage can also be minimized.

[0098] Film shrinkage can contribute to various undesirable effects. For example, if the exposed area shrinks significantly, it can lead to high dose-to-size (DtS), limiting the applicability of the resist as an etching hard mask. Thus, the films herein can be used to avoid film shrinkage. Such films can, for example, reduce DtS after subsequent development and / or use as an etching hard mask.

[0099] Radiation absorption can also be improved. For example, a smaller size of the radiation cleavable group provides a denser membrane, thereby providing additional atoms for radiation absorption (e.g., cm -2 Based on. In addition, halogen atoms have a higher EUV absorption rate compared to hydrogen atoms. Thus, the presence of halogen substituents on the radiation cleavable group can provide EUV-sensitive moieties with increased absorption. In other embodiments, haloaliphatic groups or halo atoms from such groups are incorporated into the film, where the halogen has a higher EUV absorption rate than hydrogen. Such groups (e.g., haloaliphatic groups or halo atoms) can be provided attached to metal atoms, bridging two metal atoms, or attached to ligands. Films with higher absorption can, for example, reduce line width roughness (LWR) after subsequent development (without requiring higher doses) and can provide thinner films that provide sufficient absorption and effective patterning without being limited to a minimum thickness. Such thin films can be processed by using optical applications with shallow depth of focus.

[0100] Described herein are precursors (e.g., metal-containing precursors and ligand-containing precursors) that can be used to provide such resist films. Generally, metal-containing precursors include a metal center (M) with additional ligands (L) and / or radiation-cleavable groups (R). In one example, the L group reacts with a back reactant to promote the formation of a metal-oxy network. In another example, the L group reacts with a ligand-containing precursor. In certain embodiments, the R group is cleavable from M by exposure to radiation. Examples of R include C 1-2 Haloalkyl, C 1-4 Haloalkyl, C 2-4 Haloalkenyl, C 2-4 Haloalkynyl, C 1-2 Alkyl, C 2-4 Alkenyl, and C 2-4 Examples include alkynyl.

[0101] FIG. 1A shows a resist film formed by using a non-limiting metal-containing precursor (I-1) containing -CH2X as an exemplary radiation cleavable group or R. Unless otherwise specified, X refers to a halo or halogen atom. The metal-containing precursor (I-1) also contains tin (Sn) as M and an additional L group. By depositing the precursor (I-1) in the presence of an oxygen-containing reverse reactant ([O]), the film contains a network of organotin hydroxide material (10). Upon exposure to EUV radiation, the exposed areas release the radiation cleavable group (here, -CH2X), thereby forming voids in the film where the -CH2X group was present. Further post-exposure treatment, such as a post-exposure bake (PEB), results in a crosslinked film having a network of tin-oxy material (12). As can be seen, after PEB, the degree of film shrinkage between the exposed film and the crosslinked film may depend on the voids present in the exposed film.

[0102] FIG. 1B shows non-limiting examples of other metal-containing precursors with different radiation cleavable groups (R groups). For example, the radiation cleavable group can be C 1-2Precursor (I-2) contains a methyl group as R, and precursor (I-6) contains an ethyl group as R. In another example, the radiation cleavable group is a C alkyl group having one, two, three, or more halo (X) substituents. 1-2 The precursors (I-3), (I-4), and (I-5) contain a halomethyl group as R. The precursors (I-7) and (I-8) contain a haloethyl group as R. In one example, the haloethyl group contains one or more halo substituents on the β carbon (the α carbon of the haloethyl is bonded to Sn). In yet another example, the radiation cleavable group is a C alkyl group such as alkenyl. 2-4 It can be an unsaturated aliphatic group. Precursor (I-9) contains an ethenyl group as R. If the precursor contains an unsaturated moiety such as ethenyl (commonly called vinyl), EUV exposure can result in a crosslinking reaction (e.g., between ligands or unsaturated groups) rather than the cleavage reaction typical of alkyl substituents. This can have the additional important advantage of further reducing film shrinkage due to EUV and post-EUV bake, thereby improving pattern fidelity.

[0103] Still other metal-containing precursors may include those having formulas (I), (Ia), (III), (IIIa), (V), (Va), (VI), (VII), (VIII), (IX), (X), (XI), etc., as described herein. Additional metal-containing precursors include CX, z H 3-z SnL3 and CX z H 3-z and each X is independently halo (F, Cl, Br, or I), z=1, 2, 3, or 4, and each L is independently halo (e.g., Cl or Br), optionally substituted amino (e.g., dialkylamino such as -N(Me)), optionally substituted alkoxy (e.g., C-alkylamino such as -OCMe), 1-4alkoxy), a ligand that reacts with a reverse reactant (e.g., reacts with water), or a ligand that reacts with a ligand-containing precursor. Other metal-containing precursors include SnL2, where each L is independently halo (e.g., Cl or Br), optionally substituted amino (e.g., dialkylamino such as -N(Me)2), optionally substituted alkoxy (e.g., C-alkylamino such as -OCMe3). 1-4 alkoxy), a ligand that reacts with a reverse reactant (e.g., reacts with water), or a ligand that reacts with a ligand-containing precursor.

[0104] Further metal-containing precursors include C n H m and SnL3, where n=1, 2, 3, or 4, and m≧1 (e.g., 1-9), and each L is independently selected from halo (e.g., Cl or Br), optionally substituted amino (e.g., dialkylamino such as -N(Me)2), optionally substituted alkoxy (e.g., C-alkylamino such as -OCMe3), 1-4 alkoxy), a ligand that reacts with a reverse reactant (e.g., reacts with water), or a ligand that reacts with a ligand-containing precursor. In certain embodiments, m=2n+1, 2n-1, or 2n-3.

[0105] The metal-containing precursor can be used alone or can be used with additional precursors, such as ligand-containing precursors, to further modify the functional groups attached to M in the metal-containing precursor. The ligand-containing precursors can react with the metal-containing precursor to introduce additional L and / or R groups onto M.

[0106] 2A shows an example of a non-limiting precursor that can react with each other to form a further precursor, which can then be deposited as a film. In certain embodiments, a precursor can be synthesized (e.g., outside the deposition chamber) using a metal-containing precursor and a ligand-containing precursor, and then the synthesized precursor can be delivered to the chamber for deposition. As can be seen, the first metal-containing precursor (IA) comprises a metal center (M), a cleavable group (R), and a ligand that comprises halo (X). The ligand-containing precursor (II-A) includes a metal or metalloid center (A) and a ligand (L", which can be, for example, any of the Ls described herein. A non-limiting example of such a precursor can be an organolithium compound, such as LiL, where A is lithium (Li). Such a precursor can be selected to provide a further metal-containing precursor. For example, precursors (IA) and (II-A) can react to form a further metal-containing precursor (IB), which can then be deposited in situ to provide a film on a substrate in the chamber. By-products include compound (II-B), which can be removed from the chamber as desired. Here, a halo group on the initial metal-containing precursor (IA) is replaced with a ligand (L") in the further metal-containing precursor (IB). In certain embodiments, the further metal-containing precursor (e.g., formed by reacting the initial metal-containing precursor with a ligand-containing precursor) can include a structure having formula (I).

[0107] FIG. 2B shows another example of non-limiting precursors that can react with each other to form further precursors. Here, such precursors can be reacted to synthesize further precursors outside of the deposition chamber (e.g., delivered to the chamber for subsequent deposition) or within the chamber (e.g., by CVD with in situ synthesis of further precursors prior to deposition). As can be seen, the initial metal-containing precursor (III-A) includes a metal center (M) and a ligand (L′, which can be, for example, any L described herein). A non-limiting example of such a metal center is tin (II). The ligand-containing precursor (IV-A) includes a cleavable group (R) and a ligand (L″, which can be, for example, any L described herein, such as halo). When such precursors (III-A) and (IV-A) react, a further metal-containing precursor (IC) is formed. Here, the ligand (L′) on the initial metal-containing precursor (IA) is retained on M, and further groups (R and L″) are provided on M to provide the further metal-containing precursor (IC). In certain embodiments, the additional metal-containing precursor (eg, formed by reacting the initial metal-containing precursor with a ligand-containing precursor) can include a structure having formula (I).

[0108] By combining such metal-containing precursors with ligand-containing precursors, it is possible to provide further metal-containing precursors. In this way, the final combination of cleavable groups (R) and / or ligands (L) can be modified either in situ (within the chamber) or prior to delivery to the chamber for deposition.

[0109] Still other ligand-containing precursors include structures having formula (II), (IIa), (IV), or (IVa) as described herein. Additional ligand-containing precursors may include organolithium compounds (e.g., LiL), organosodium compounds (e.g., NaL), organomagnesium compounds (e.g., MgL2), Grignard reagents (e.g., MgLX, where X is halo), organozinc compounds (e.g., ZnL2), or organoaluminum compounds (e.g., AlL3). In certain embodiments, such reagents are not used in the deposition chamber, but are used to synthesize the precursor before it is delivered to the deposition chamber.

[0110] Useful ligands in the ligand-containing precursors can include any of those described herein, including organic moieties (e.g., optionally substituted alkyl, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiMe3)2), optionally substituted trialkylsilyl, etc.). Other ligand-containing precursors can include aliphatic halides (e.g., Rx, where X is halo and R is an optionally substituted alkyl) or haloaliphatic halides (e.g., Rx, where X is halo and R is an optionally substituted haloalkyl). Non-limiting R groups include optionally substituted C 1-2 Haloalkyl, e.g. -CX z H 3-z Or -CH2CX z H 3-z , z is 1, 2, or 3; and optionally substituted C 1-4 Alkyl, e.g. -C n H 2n+1 , n is 1 or 2; or for example -C n H 2n-1 or -C n H 2n-3 , n is 2, 3, or 4.

[0111] The present disclosure also generally includes any useful method of using metal-containing precursors with optional ligand-containing precursors as described herein. Such methods can include any useful lithography, deposition, radiation exposure, development, and post-application processes as described herein. Although techniques related to EUV processes may be described below, such techniques may also be applicable to other next-generation lithography techniques. A variety of radiation sources can be used, including EUV (typically around 13.5 nm), DUV (deep UV, typically in the 248 nm or 193 nm range with excimer laser sources), X-ray (including EUV in the lower energy range of the X-ray range), and e-beam (including a wide energy range).

[0112] Exemplary methods can include delivering a metal-containing precursor to a substrate, and simultaneously or sequentially delivering a metal-containing precursor and a ligand-containing precursor to the substrate. For example, Figure 3A shows a non-limiting method 300 that includes depositing 301 a metal-containing precursor 30 and an optional ligand-containing precursor 32 on a substrate 311. Such co-deposition can provide a dense halogenated film 312 having a matrix of metal atoms and (halo)aliphatic components. Such deposition can include dry deposition.

[0113] When a ligand-containing precursor is used, the delivery of the metal-containing precursor and the ligand-containing precursor can be in any useful order. When delivered sequentially, an optional operation can include purging the chamber to remove unreacted precursor. Such purging can include the use of an inert gas to remove metal-containing precursor or ligand-containing precursor that is present in vapor form and thus has not been deposited on the substrate.

[0114] Such films can be deposited in any useful manner described herein. Exemplary deposition techniques include chemical vapor deposition (CVD), plasma-enhanced CVD (PE-CVD), low pressure CVD (LP-CVD), atomic layer deposition (ALD) (e.g., thermal ALD and plasma-enhanced ALD (PE-ALD)), molecular layer deposition (MLD), spin-coat deposition, physical vapor deposition (PVD) including PVD co-sputtering, sputter deposition, electron beam (e-beam) deposition including e-beam co-evaporation, and the like, or combinations thereof. Other deposition processes and conditions are described herein.

[0115] The metal-containing precursor and / or the ligand-containing precursor can be optionally deposited in the presence of one or more reverse reactants. The reverse reactant preferably has the ability to replace a reactive moiety, ligand, or ion (e.g., L in the formulas herein) to link at least two metal atoms via a chemical bond. Exemplary reverse reactants include oxygen-containing reverse reactants, such as O2, O3, water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, dihydroxy or polyhydroxy alcohols, fluorinated dihydroxy or polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, and combinations thereof. In various embodiments, the reverse reactant reacts with the metal-containing precursor and / or the ligand-containing precursor by forming oxygen bridges between adjacent metal atoms. Other potential reverse reactants include hydrogen sulfide and hydrogen disulfide, which can bridge metal atoms via sulfur bridges, and bis(trimethylsilyl)tellurium, which can bridge metal atoms via tellurium bridges. In addition, hydrogen iodide may be utilized to incorporate iodine into the film. Still other reverse reactants may include any of the chalcogenide-containing precursors or chalcogenide-containing compounds described herein.

[0116] Various process conditions for deposition can be modified and optimized. For example, deposition (e.g., of metal-containing precursors and / or ligand-containing precursors) can be performed at temperatures of about 20-400°C, such as about 50-300°C, about 100-200°C, or about 150°C. In some embodiments, the metal-containing precursors and / or ligand-containing precursors have a thermal decomposition point higher than the process temperature to cause a self-limiting surface reaction. Non-limiting pressure conditions include a range of about 0.1-50 Torr, such as about 1-15 Torr. In some embodiments, the metal-containing precursors and / or ligand-containing precursors have a vapor pressure of greater than 0.5 Torr at or below 100°C.

[0117] Process step times for each operation can include the following ranges: about 0.1 to 10 seconds for the metal-containing precursor dosage, about 0.1 to 60 seconds for the ligand-containing precursor dosage, and about 0.1 to 60 seconds for the purge period.

[0118] The deposition can be repeated for any number of cycles. Each cycle can include a deposition operation that can include deposition of a metal-containing precursor, co-deposition of a metal-containing precursor and a ligand-containing precursor, or sequential deposition of a metal-containing precursor and a ligand-containing precursor with an optional purge operation. Such cycles can be repeated for any useful number of cycles, for example, 1 to 1000 cycles, to deposit a desired film thickness.

[0119] Once a desired film thickness has been deposited, a post-deposition treatment step may be performed. In one example, such post-deposition treatment involves exposing the film to a dosing (or soaking) for an extended period of time with a soaking precursor. Soaking may be used to increase the EUV absorbance of the film. In one embodiment, the soaking precursor is a metal-containing precursor, and the use of the soaking precursor increases the concentration of metal atoms in the film. In other embodiments, the soaking precursor is a ligand-containing precursor. The soaking precursor may be the same or different from the metal-containing precursor used in the deposition process. The soaking may be performed under similar conditions as the deposition process, although the dosing time may generally be relatively long, such as in the range of 30 seconds to 30 minutes.

[0120] The methods herein can include deposition directly on the substrate or deposition on a layer disposed on a surface of the substrate. In one example, the substrate can include an adhesion layer or underlayer, which can be an organic underlayer or an intermediate etch layer.

[0121] The resist film can have any useful structure. In one embodiment, the film has a thickness of about 0.5 nm to about 100 nm (e.g., about 5 nm to 100 nm, as well as other thicknesses described herein). The film can include an optional underlayer or an optional surface activation step prior to deposition of the metal-containing precursor.

[0122] The film can have a vertical gradient characterized by a vertical change in EUV absorbance. In some cases, an increase in EUV absorbance along the depth (e.g., from the top surface of the film toward the substrate) can correspond to an increase in metal or halogen content along the same depth through the film layer. Non-limiting gradients include linear gradients, exponential gradients, sigmoidal gradients, and the like. In certain embodiments, a gradient density film of EUV reactive moieties can result in more homogeneous film properties of the EUV-exposed regions at all depths within the film, which may improve the development process, improve EUV sensitivity, and / or improve patterning quality (e.g., having improved line width roughness (LWR) and / or line edge roughness (LER)).

[0123] The resist film is made of organometallic materials, such as organometallic oxides (e.g., RM(MO) n , M is a metal and R is a halogenated organic moiety having one or more carbon atoms and one or more halogen atoms). The substrate can include any useful wafer, feature, layer, or device. In some embodiments, the substrate is a silicon wafer having any useful feature (e.g., irregular surface topography), layer (e.g., a photoresist layer), or device.

[0124] The radiation sensitive film can include metal components and organic substituents, each of which can include UV, DUV, or EUV sensitive moieties. Non-limiting examples of these include, for example, 1×10 7 cm 2 The constituent may be a metal or metalloid or an atom having a high EUV absorption cross section, such as 10 ...

[0125] The film can be homogenous. In certain embodiments, the homogenized matrix can be an alloy film. The co-deposition can be performed by any useful methodology (e.g., CVD) using the co-flow of both metal-containing and ligand-containing precursors.

[0126] The resulting film can be used as a photoresist. In certain non-limiting embodiments, the layer can include moieties that promote radiation absorption after radiation exposure (e.g., exposure to UV, DUV, and / or EUV radiation). In further embodiments, the organometallic layer can include metal centers and halogen atoms that promote radiation absorption. After deposition, the film can be patterned by radiation exposure and then developed, thereby providing a negative or positive resist. Such methods can include any useful lithography process, deposition process, EUV exposure process, development process, and post-application process described herein. In certain embodiments, the film exhibits minimal film shrinkage after EUV exposure, development, and / or post-application processes.

[0127] Returning to Figure 3A, a further step may include patterning the film with an EUV exposure 302 to provide an exposed film having EUV exposed regions 312b and EUV non-exposed regions 312c. The patterning may include the use of a mask 314 having EUV transparent and EUV opaque regions, where an EUV beam 315 is transmitted through the EUV transparent regions to the film 312. The EUV exposure may include, for example, an exposure having a wavelength in a range of about 10 nm to about 20 nm in a vacuum atmosphere (e.g., about 13.5 nm in a vacuum atmosphere).

[0128] The method 300 may further include developing 303 the film, thereby either (i) removing the EUV-exposed regions to provide a pattern in the positive resist film, or (ii) removing the EUV-unexposed regions to provide a pattern in the negative resist film. Path (i) in Figure 3A selectively removes the EUV-exposed regions 312b. Alternatively, path (ii) in Figure 3A maintains the EUV-exposed regions 312b after development.

[0129] The developing step can include the use of halide chemistries (e.g., HBr chemistries) in the gas phase, or aqueous or organic solvents (e.g., as described herein) in the liquid phase. The developing step can include any useful experimental conditions, such as low pressure conditions (e.g., about 1 to about 100 mTorr), plasma exposure (e.g., in the presence of a vacuum), and / or thermal conditions (e.g., about -10°C to 100°C) that can be combined with any useful chemistries (e.g., halide or aqueous chemistries). The developing can include, for example, a halide-based etchant, such as HCl, HBr, H2, Cl2, Br2, BCl3, or combinations thereof, as well as any halide-based developing process described herein, an aqueous alkaline developing solution, or an organic developing solution. Additional developing process conditions are described herein.

[0130] Optional steps may be performed to further condition, modify, or treat the EUV sensitive film, substrate, photoresist layer, and / or in any of the methods herein. Figure 3B shows a flow chart of an exemplary method 350 having various operations, including optional operations. As can be seen, in operation 354, a metal-containing precursor and an optional ligand-containing precursor are provided in the presence of an optional back-reactant to provide a resist film (e.g., in a chamber).

[0131] In one example, the method can include an optional step 356 of cleaning the backside or bevel of the substrate or removing an edge bead of photoresist deposited in a previous step. Such a cleaning or removal step can be useful to remove particles that may be present after depositing a membrane layer. The removal step can include treating the wafer with a wet metal oxide (MeOx) edge bead removal (EBR) step.

[0132] In another example, the method can include an optional step 358 of performing a post-apply bake (PAB) of the deposited photoresist layer to remove residual moisture from the layer to form a film or pretreat the photoresist layer in any useful manner. The optional PAB can be performed after film deposition and prior to EUV exposure, and the PAB can involve a combination of heat treatment, exposure to chemicals, and moisture to increase the EUV sensitivity of the film, thereby reducing the EUV dose 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 100-200° C., or between 100-250° C. In some cases, PAB is not performed within the method.

[0133] In operation 360, the film is exposed to EUV radiation to develop the pattern. Generally, the EUV exposure causes a change in the chemical composition of the film, creating an etch selectivity contrast that can be used to remove portions of the film. Such contrast can provide a positive or negative resist as described herein.

[0134] In yet another example, the method can include an optional step 362 of performing a post-exposure bake (PEB) of the exposed film to further remove residual moisture, promote chemical condensation in the film, or post-treat the film in any useful manner. In another example, the method can include hardening the patterned film (e.g., after development) to provide a resist mask disposed on top of the substrate. The hardening step can include any useful process that further crosslinks or reacts the EUV non-exposed or EUV exposed regions, such as exposure to plasma (e.g., O2, Ar, He, or CO2 plasma), exposure to ultraviolet radiation, annealing (e.g., at a temperature of about 180° C. to about 240° C.), thermal baking, or combinations thereof that may be useful for a post-development bake (PDB) step. Additional post-application processes are described herein and can be performed as optional steps to any of the methods described herein.

[0135] The PR pattern is then developed in operation 364. In various embodiments of development, either the exposed areas are removed (positive tone) or the unexposed areas are removed (negative tone). In various embodiments, these steps may be dry and / or wet processes.

[0136] In some embodiments, the process includes an all-dry process, including dry deposition of a film (e.g., using a precursor in vapor form and a reverse reactant including water vapor) and dry development of the exposed film. Without wishing to be limited by mechanism, such a film can provide a negative resist, where radiation-exposed areas provide non-volatile material and radiation-unexposed areas provide volatile by-products upon exposure to dry development chemistry (e.g., vapor-based etchant chemistry as described herein). In this manner, an etchant in the vapor phase can be used to react with the unexposed film to provide volatile by-products, which can also be removed in vapor form.

[0137] In other embodiments, wet processes can be used in one or more operations. Such processes can include dry deposition of a film (e.g., with a precursor in vapor form and a reverse reactant including water vapor) and wet development of the exposed film (e.g., using any of the wet developers described herein), as well as wet deposition of a film (e.g., with a precursor in a solvent) and dry development of the exposed film, as well as wet deposition of a film with wet development of the exposed film. Without wishing to be limited by mechanism, such a film can provide a positive resist, where the radiation exposed areas provide a material that can be dissolved in a solvent (e.g., includes metal halide bonds such as tin halide) and the radiation areas provide a material that is more resistant to dissolution by the solvent.

[0138] 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 chemicals in the gas phase or wet processes using chemicals in the wet phase. Various embodiments include combining all dry operations of film formation by gas phase deposition, (EUV) lithography photopatterning, dry stripping, and dry development. Various other embodiments include the dry processing operations described herein advantageously combined with wet processing operations, e.g., spin-on EUV photoresist (wet process) such as those available from Inpria Corp., which can be combined with dry development or other wet or dry processes described herein. In various embodiments, the 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.

[0139] Without limiting the mechanism, function, or utility of the present technology, the dry process of the present technology can provide various advantages over wet development processes known in the art. For example, the dry vapor deposition techniques described herein can be used to deposit thinner, defect-free 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. Thus, dry processes can provide more adjustability and give additional critical dimension (CD) control and scum removal. Dry development can improve performance (e.g., preventing line collapse due to surface tension in wet development) and / or increase throughput (e.g., by avoiding wet development tracks). Other advantages can include eliminating the use of organic solvent developers, reducing sensitivity to adhesion problems, avoiding the need to apply and remove wet resist formulations (e.g., avoiding scum and pattern distortion), improving line edge roughness, patterning directly over device topography, providing the ability to tailor hardmask chemistry to specific substrates and semiconductor device designs, and avoiding other solubility-based limitations. Additional details, materials, processes, steps, and apparatus are described herein.

[0140] Metal-Containing Precursors The metal-containing precursor can have any useful number and type of cleavable groups and / or ligands. The cleavable groups can be characterized by their ability to react in the presence of patterning radiation, and the ligands can be characterized by their ability to react in the presence of a counter reactant. For example, the metal-containing precursor can include a cleavable group that leaves in the presence of patterning radiation. Such groups include C 1-4 In another example, the metal-containing precursor may include a ligand (e.g., a dialkylamino group or an alkoxy group) that reacts with a reverse reactant, which can introduce a linkage (e.g., an -O- linkage) between the metal centers.

[0141] The metal-containing precursor can be, for example, an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In a non-limiting example, the metal-containing precursor has the formula (I): M a R b L c (I)

[0023] each M is independently a metal or a metalloid; Each R is independently an optionally substituted C 1-4 Haloaliphatic or C 1-4 It is aliphatic, each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety reactive with a back-reactant and / or a ligand-containing precursor; a≧1, b≧1, and c≧1. In certain embodiments of Formula (I), a is 1, 2, or 3. In further embodiments, b is 1, 2, 3, 4, 5, or 6 and c is 1, 2, 3, 4, 5, or 6.

[0142] In some embodiments, the metal-containing precursor has formula (Ia): SnR b L 3-b (Ia) containing tin(IV), such as having the structure Each R is independently an optionally substituted C 1-4 Haloaliphatic or C 1-4 It is aliphatic, each L is independently halo, optionally substituted amino, optionally substituted alkoxy, or a ligand that reacts with a reverse reactant and / or a ligand-containing precursor; b is 1 or 2.

[0143] In some embodiments, M is a high patterning radiation absorption cross section (e.g., 1×10 7 cm 2 / mol).

[0144] In some embodiments, the metal-containing precursor (e.g., in Formula (I), (Ia), (IV), (IVa), or any other formula herein) comprises at least one optionally substituted C 1-2 Non-limiting examples of haloaliphatic groups include -CX y H 3-y , y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I);-CX z H 2-z CX y H 3-y , z is 0, 1, or 2, y is 0, 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I), and at least one of z or y is not 0; or -CHCX y H 3-y , y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I). Still other non-limiting haloalkyl groups include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (-CH2Cl), dichloromethyl (-CHCl2), trichloromethyl (-CCl3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (-CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoromethyl (-CHFBr), chloro ...Cl), chlorofluoromethyl (-CHCl), chlorofluoromethyl (-CHBr), bromomethyl (-CHBr), dibromomethyl (-CHBr), tribromomethyl (-CHBr), tribromomethyl (-CBr), iodomethyl (-CH2I), diiodomethyl ethyl (-CHFCl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CHCHF), 2-chloroethyl (-CHCHCl), 2-bromoethyl (-CHCHBr), 2-iodoethyl (-CHCHI), 2,2-difluoroethyl (-CHCHF), 2,2-dichloroethyl (-CHCHCl), 2,2-dibromoethyl (-CHCHBr), 2,2-diiodoethyl (-CHCHI), 2,2-fluoroiodoethyl (-CHCHFI), and the like. In certain embodiments, C 1-2Haloalkyl includes β-halo substituted ethyl. Further haloaliphatic groups include C 1-4 Haloalkyl, C 2-4 Haloalkenyl, and C 2-4 Haloalkynyl is mentioned.

[0145] In other embodiments, the metal-containing precursor (e.g., in Formula (I), (Ia), (IV), (IVa), or any other formula herein) comprises at least one optionally substituted C 1-2 Alkyl groups, optionally substituted C 2-4 alkenyl, or optionally substituted C 2-4 Non-limiting groups include -C n H 2n+1 , n is 1 or 2;-C n H 2n-1 , n is 2, 3, or 4; or -C n H 2n-3 , where n is 2, 3, or 4. Still other non-limiting groups include methyl (-CH3), ethyl (-CH2CH3), vinyl or ethenyl (-CH=CH2), 1-propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (e.g., -CH2CH2CH=CH2), ethynyl (-C≡CH), 1-propynyl (-C≡CCH3), 2-propynyl or propargyl (-CH2C≡CH), 1-butynyl (-C≡CCH2CH3), 2-butynyl (-CH2C≡CCH3), 3-butynyl (-CH2CH2C≡CH), and the like.

[0146] In some embodiments, each ligand in the metal-containing precursor can be a ligand that reacts with a counter reactant and / or a ligand-containing precursor. In one example, the metal-containing precursor comprises a structure having formula (I), where each R is independently L. In another example, the metal-containing precursor comprises a structure having formula (III): M a L c (III)

[0023] each M is independently a metal; each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety reactive with a back-reactant and / or a ligand-containing precursor; a≧1, and c≧1. In certain embodiments of Formula (III), a is 1. In further embodiments, c is 2, 3, or 4.

[0147] In other embodiments, the metal-containing precursor has the formula (IIIa): SnL2(IIIa)

[0023] Each L is independently halo, optionally substituted amino, optionally substituted alkoxy, or a ligand that reacts with a reverse reactant and / or a ligand-containing precursor.

[0148] For any formula herein, M is a high patterning radiation absorption cross section (e.g., 1×10 7 cm 2 M may be a metal having an EUV absorption cross section of 1000 nm / mol or more. In some embodiments, M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), hafnium (Hf), or zirconium (Zr). In further embodiments, in formula (I), M is Sn, a is 1, and b+c is 4. In other embodiments, in formula (I), M is Sn, a is 1, and b+c is 2. In yet other embodiments, in formula (III), M is Sn, a is 1, and c is 2. In certain embodiments, M is Sn(II) (e.g., in formula (I) or (III)), thereby providing a metal-containing precursor that is a Sn(II)-based compound. In other embodiments, M is Sn(IV) (e.g., in formula (I) or (III)), thereby providing a metal-containing precursor that is a Sn(IV)-based compound.

[0149] For any formula herein, 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 (e.g., -OR 1 , R 1 In some embodiments, an optionally substituted amino is -NR 1 R 2 And 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, and each R 1 , R 2 , and R 3 is independently alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR 1 R 2 R 3 And each R 1 , R 2 , and R 3 is independently alkyl.

[0150] In other embodiments, the formula is -NR 1 R 2 The first L and -NR 1 R 2 Each R 1 and R 2 is independently H or alkyl, or the first L to R 1 and R from the second L 1taken together with the nitrogen atom and metal atom to which each is attached, form a heterocyclyl group as defined herein. 1 The first L and -OR 1 Each R 1 is independently H or alkyl, or the first L to R 1 and R from the second L 1 together with the oxygen atom and metal atom to which each is attached form a heterocyclyl group, as defined herein.

[0151] In some embodiments, at least one of L or R is an optionally substituted alkyl (e.g., in formula (I), (Ia), (III), or (IIIa)). Non-limiting alkyl groups include, for example, C n H 2n+1 where n is 1, 2, 3 or more, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. In various embodiments, L or R has at least one beta hydrogen or beta halogen.

[0152] In some embodiments, at least one of L or R is an optionally substituted haloalkyl (e.g., in formula (I), (Ia), (III), or (IIIa)). Non-limiting haloalkyl groups include, for example, C n H 2n+1-z X zwhere n is 1, 2, 3, or more, z is 1 to 2n+1 (e.g., 1 to 3, 1 to 5, or 1 to 7), and each X is independently halo (F, Cl, Br, or I). In various embodiments, L or R has at least one beta hydrogen and / or beta halogen. In particular, the metal-containing precursor can be FCH2SnL3, CF3SnL3, ICH2SnL3, CI3SnL3, CH2FCH2SnL3, or CH2ICH2SnL3, where each L can be any described herein (e.g., including halo, optionally substituted amino, or optionally substituted alkoxy).

[0153] In some embodiments, at least one of L or R is an optionally substituted alkenyl or an optionally substituted alkynyl (e.g., in formula (I), (Ia), (III), or (IIIa)). Non-limiting alkenyl groups include, for example, C n H 2n-1 where n is 2, 3, 4 or more, such as ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, or 3-butenyl. Non-limiting alkynyl groups include, for example, C n H 2n-3 where n is 2, 3, 4 or more, for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, or 3-butynyl.

[0154] In some embodiments, each L or at least one L is halo (e.g., in formula (I), (Ia), (III), or (IIIa)). In particular, the metal-containing precursor can be a metal halide or an organometallic halide. Non-limiting metal halides and organometallic halides include FCH2SnX3, CF3SnX3, ICH2SnX3, CI3SnX3, CH2FCH2SnX3, CH2ICH2SnX3, SnX2, or SnX4, where each X is independently halo. In other embodiments, the metal-containing precursor is RSnX3, where R is C 1-4 Haloalkyl, C 2-4Haloalkenyl, or C 2-4 In yet another embodiment, the metal-containing precursor is RSnX3, where R is C 1-2 Alkyl, C 2-4 Alkenyl, or C 2-4 alkynyl and each X is independently halo.

[0155] In some embodiments, each L or at least one L can include a nitrogen atom. In certain embodiments, one or more L can be optionally substituted amino or optionally substituted bis(trialkylsilyl)amino (e.g., in formula (I), (Ia), (III), or (IIIa)). Non-limiting L substituents can include, for example, -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)-(tbba), -N(SiMe3)2, and -N(SiEt3)2. Non-limiting metal-containing precursors include, for example, Sn(CH2F)(NMe2)3, Sn(CF3)(NMe2)3, Sn(CH2I)(NMe2)3, Sn(Cl3)(NMe2)3, Sn(CH2CH2F)(NMe2)3, Sn(CH2CH2I)(NMe2)3, Sn(CH2F)2(NMe2)2, Sn(CF3)2(NMe2)2, Sn(CH2I)2(NMe2)2, Sn(Cl3)2(NMe2)2, Sn(CH2CH2F)2(NMe2)2, Sn(CH2CH2I)2(NMe2)2, Sn(CH2F)(NEt2)3, Sn(CF3)(NEt2)3, Sn (CH2I)(NEt2)3, Sn(Cl3)(NEt2)3, Sn(CH2CH2F)(NEt2)3, Sn(CH2CH2I)(NEt2)3, Sn(CH3)(NMe2)3, Sn(CH2CH3)(NMe2)3, Sn(CH=CH2)(NMe2)3, Sn(CH=CHCH3)(NMe2)3, Sn(CH2-CH=CH2)(NMe2)3, Sn(C≡CH)(NMe2)3, Sn(C≡CCH3)(NMe2)3, Sn(CH2C≡CH)(NMe2)3, Sn(NMe2), Sn(NEt2)2, or Sn[N(SiMe3)2]2.

[0156] In some embodiments, the metal-containing precursor is RSn(NMe2)3, RSn(NMe2)2(NEt2), RSn(NEt2)3, or RSn[N(SiMe3)2]3, where R is C 1-2 Haloalkyl, C 2-4 Haloalkenyl, C 2-4 Haloalkynyl, C 1-2 Alkyl, C 2-4 Alkenyl, or C 2-4 In other embodiments, the metal-containing precursor is R2Sn(NMe2)2, R2Sn(NMe2)(NEt2), R2Sn(NEt2)2, or R2Sn[N(SiMe3)2]2, where each R is independently C 1-2 Haloalkyl, C 2-4 Haloalkenyl, C 2-4 Haloalkynyl, C 1-2 Alkyl, C 2-4 Alkenyl, or C 2-4 It is alkynyl.

[0157] In another embodiment, the metal-containing precursor is RSnL3, where R is C 1-2 Haloalkyl, C 2-4 Haloalkenyl, C 2-4 Haloalkynyl, C 1-2 Alkyl, C 2-4 Alkenyl, or C 2-4 alkynyl, and each L is independently selected from the group: -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)-(tbba), -N(SiMe3)2, and N(SiEt3)2.

[0158] In yet other embodiments, the metal-containing precursor is SnL2, where each L is independently selected from the group of -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)-(tbba), -N(SiMe3)2, and N(SiEt3).

[0159] In some embodiments, each L or at least one L can include a silicon atom. In certain embodiments, one or more L can be an optionally substituted trialkylsilyl or an optionally substituted bis(trialkylsilyl)amino (e.g., in formula (I)(Ia), (III), or (IIIa)). Non-limiting L substituents can include, for example, -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2. Non-limiting metal-containing precursors can include, for example, Sn[N(SiMe3)2]2, bis(trimethylsilyl)tellurium (Te(SiMe3)2), bis(triethylsilyl)tellurium (Te(SiEt3)2), or Bi[N(SiMe3)2]3.

[0160] In some embodiments, each L or at least one L can include an oxygen atom. In certain embodiments, one or more L can be an optionally substituted alkoxy (e.g., in formula (I)(Ia), (III), or (IIIa)). Non-limiting L substituents include, for example, methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), and -O=C(CH3)-CH=C(CH3)-O-(acac). Non-limiting metal-containing precursors include, for example, Sn(CH2F)(t-BuO)3, Sn(CF3)(t-BuO)3, Sn(CH2I)(t-BuO)3, Sn(Cl3)(t-BuO)3, Sn(CH2CH2F)(t-BuO)3, Sn(CH2CH2I)(t-BuO)3, Sn(CH2F)2(t-BuO)2, Sn(CF3)2(t-BuO)2, Sn(CH2I)2(t-BuO)2, Sn(Cl3)2(t-BuO)2, Sn(CH2CH2F)2(t-BuO)2 BuO)2, Sn(CH2CH2I)2(t-BuO)2, Sn(t-BuO)2, Sn(CH3)(t-BuO)3, Sn(CH2CH3)(t-BuO)3, Sn(CH=CH2)(t-BuO)3, Sn(CH=CHCH3)( t-BuO)3, Sn(CH2-CH=CH2)(t-BuO)3, Sn(C≡CH)(t-BuO)3, Sn(C≡CCH3)(t-BuO)3, Sn(CH2C≡CH)(t-BuO)3, or Sn(acac)2.

[0161] In some embodiments, the metal-containing precursor is RSn(t-BuO)3, where R is C 1-2 Haloalkyl, C 2-4 Haloalkenyl, C 2-4 Haloalkynyl, C 1-2 Alkyl, C 2-4 Alkenyl, or C 2-4 In another embodiment, the metal-containing precursor is R2Sn(t-BuO)2, where each R is independently C 1-2 Haloalkyl, C 2-4 Haloalkenyl, C 2-4 Haloalkynyl, C 1-2 Alkyl, C 2-4 Alkenyl, or C 2-4 In yet another embodiment, the metal-containing precursor is RSnL3, where R is C 1-2 Haloalkyl, C 2-4 Haloalkenyl, C 2-4 Haloalkynyl, C 1-2 Alkyl, C 2-4 Alkenyl, or C 2-4 alkynyl, and each L is independently selected from the group of methoxy, ethoxy, i-PrO, and t-BuO.

[0162] Further metal-containing precursors and non-limiting substituents (e.g., R and L) are described herein. For example, the metal-containing precursor can be any of the structures of formula (I), (Ia), (III), or (IIIa) described above, or formula (V), (Va), (VI), (VII), (VIII), (IX), (X), or (XI) described below. Any of the substituents M, R, X, or L described herein can be used in any of formulas (I), (Ia), (II), (IIa), (III), (IIIa), (IV), (IVa), (V), (Va), (VI), (VII), (VIII), (IX), (X), or (XI). For example, any of the substituents M, R, X, or L described herein for (II), (IIa), (IV), (IVa), (V), (Va), (VI), (VII), (VIII), (IX), (X), or (XI) can be used in any of formulas (I), (Ia), (III), or (IIIa).

[0163] In one non-limiting example, a ligand-containing precursor can be used to react with or replace the ligand of a metal-containing precursor to provide a film. Non-limiting ligand-containing precursors are described herein.

[0164] Such precursors can be further used in combination with one or more reverse reactants. The reverse reactant preferably has the ability to replace reactive moieties, ligands, or ions (e.g., L in the formulas herein) to link at least two metal atoms via a chemical bond. Exemplary reverse reactants include oxygen-containing reverse reactants, such as O2, O3, water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, dihydroxy or polyhydroxy alcohols, fluorinated dihydroxy or polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, and combinations thereof. In various embodiments, the reverse reactant reacts with the metal-containing precursor and / or the ligand-containing precursor by forming oxygen bridges between adjacent metal atoms. Other potential reverse reactants include hydrogen sulfide and hydrogen disulfide, which can bridge metal atoms via sulfur bridges, and bis(trimethylsilyl)tellurium, which can bridge metal atoms via tellurium bridges. In addition, hydrogen iodide may be utilized to incorporate iodine into the film.

[0165] In certain embodiments, the reverse reactant may be, for example, a compound of formula (XII): X 3 -ZX 4 (XII) a chalcogenide precursor comprising a structure having the formula: Z is sulfur, selenium, or tellurium; X 3 and X 4 Each of is independently H, optionally substituted alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc.), optionally substituted alkenyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or optionally substituted trialkylsilyl.

[0166] The metal-containing precursors herein can be used to form gradient films. For example, various atoms present in the metal-containing precursor, ligand-containing precursor, and / or reverse reactant can be delivered in the gradient film. In some embodiments of the techniques described herein, a non-limiting strategy that can further improve EUV sensitivity in a photoresist (PR) film is to form a film in which the film composition is vertically graded, resulting in a depth-dependent EUV sensitivity. A homogeneous PR with a high absorption coefficient will have a reduced light intensity throughout the film's depth, requiring a higher EUV dose to ensure that the bottom is adequately exposed. By increasing the density of atoms with high EUV absorptivity at the bottom of the film relative to the top of the film (i.e., by forming a gradient with increasing EUV absorption), it is possible to more efficiently use the available EUV photons, while distributing the absorption (and secondary electron effects) more evenly toward the more highly absorbing bottom of the film. 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).

[0167] Strategies to engineer vertical compositional gradients in PR films are particularly applicable to dry deposition methods such as CVD and ALD, and can be achieved by adjusting the flow ratios between different reactants during deposition. Types of compositional gradients that can be engineered include ratios between different highly absorbing metals, the proportion of metal atoms with EUV-cleavable organic groups, the proportion of (halo)aliphatic substituents and / or back reactants that contain highly absorbing elements, and combinations of the above.

[0168] Compositional gradients in EUV PR films can also provide additional benefits. For example, a high density of highly EUV absorbing elements at the bottom of the film can effectively generate more secondary electrons that can better expose the top of the film. In addition, such compositional gradients can also 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, the incorporation of tin precursors with four leaving groups is possible, which promotes the formation of Sn-O-substrate bonds at the interface to improve adhesion.

[0169] Such gradient films can be formed by using any of the metal-containing precursors (e.g., tin or non-tin precursors), ligand-containing precursors, and / or back reactants described herein. Still other films, methods, precursors, and other compounds are described in U.S. Provisional Patent Application No. 62 / 909,430, filed October 2, 2019, entitled SUBSTRATE SURFACE MODIFICATION WITH HIGH EUV ABSORBERS FOR HIGH PERFORMANCE EUV PHOTORESISTS, and International Application No. PCT / US20 / 70172, filed June 24, 2020, entitled PHOTORESIST WITH MULTIPLE PATTERNING RADIATION-ABSORBING ELEMENTS AND / OR VERTICAL COMPOSITION GRADIENT, the disclosures of which at least relate to the composition, deposition, and patterning of direct photopatternable metal oxide films to form EUV resist masks, are incorporated herein by reference.

[0170] Furthermore, two or more different precursors can be used within each layer (e.g., membrane or capping layer). For example, two or more of any metal-containing precursors herein can be used to form an alloy. In one non-limiting example, tin tellurides can be formed by using a tin precursor containing -NR2 ligands with RTaH, RTaD, or TeR2 precursors, where R is alkyl, particularly t-butyl or i-propyl. In another example, metal tellurides can be formed by using a first metal precursor containing an alkoxy or halo ligand (e.g., SbCl3) with a tellurium-containing precursor containing a trialkylsilyl ligand (e.g., bis(trimethylsilyl)tellurium).

[0171] Still other exemplary EUV-sensitive materials, as well as processing methods and apparatus, are described in U.S. Pat. No. 9,996,004 and International Patent Publication No. WO2019 / 217749, each of which is incorporated herein by reference in its entirety.

[0172] Ligand-Containing Precursors The ligand-containing precursor can be any that has a ligand (e.g., reacts with a reverse reactant and / or a metal-containing precursor). In one embodiment, such a ligand-containing chemical is generally used prior to the film deposition process to prepare a suitable metal-containing precursor. For example, the ligand-containing precursor can include a structure having formula (II) or (IIa), which can react with the metal-containing precursor (e.g., a structure having formula (I)) to exchange the ligand.

[0173] In one embodiment, the ligand-containing precursor has formula (II): A d L e (II)

[0023] each A is independently a metal or metalloid (e.g., lithium (Li), sodium (Na), magnesium (Mg), zinc (Zn), or aluminum (Al)); each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety reactive with a reverse reactant and / or a metal-containing precursor; d≧1 (e.g., d is 1, 2, or 3), and e≧1 (e.g., e is 1, 2, 3, 4, 5, 6, 7, or 8).

[0174] In yet another embodiment, the ligand-containing precursor has the formula (IIa): AL e (IIa)

[0023] each A is independently a metal or metalloid (e.g., Li, Na, Mg, Zn, or Al); each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety reactive with a reverse reactant and / or a metal-containing precursor; e≧1 (e.g., e is 1, 2, or 3).

[0175] In certain embodiments, the ligand-containing precursor is an organolithium compound (e.g., LiL), an organosodium compound (e.g., NaL), an organomagnesium compound (e.g., MgL2), a Grignard reagent (e.g., MgLX, where X is halo), an organozinc compound (e.g., ZnL2), or an organoaluminum compound (e.g., AlL3). In some embodiments, L is any ligand (e.g., as R or L) described herein for Formula (I), (Ia), (III), (IIIa), (V), (Va), (VI), (VII), (VIII), (IX), (X), or (XI).

[0176] In another embodiment, the ligand-containing precursor can be used to synthesize a precursor (prior to deposition) or provide a precursor in situ (e.g., during deposition in the chamber). For example, the ligand-containing precursor can include a structure having formula (IV) or (IVa) and can be reacted with a metal-containing precursor (e.g., a structure having formula (I), (Ia), (III), or (IIIa)). In some embodiments, the metal-containing precursor includes tin (II). In other embodiments, a metal-containing precursor including formula (III) reacts with a ligand-containing precursor including formula (IV) to provide a precursor including a structure having formula (I).

[0177] In some embodiments, the ligand-containing precursor includes both an R group and an L group. In one embodiment, the ligand-containing precursor has formula (IV): R f L g (IV)

[0023] Each R is independently an optionally substituted C 1-4 Haloaliphatic or C 1-4 It is aliphatic, each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety reactive with a reverse reactant and / or a metal-containing precursor; f ≧1 (e.g., 1, 2, or 3), and g > 1 (e.g., 1, 2, 3, 4, or 5).

[0178] In other embodiments, the ligand-containing precursor has formula (IVa): RL(IVa)

[0023] Each R is independently an optionally substituted C 1-4 Haloaliphatic or C 1-4 It is aliphatic, Each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety that reacts with a reverse reactant and / or a metal-containing precursor. In certain embodiments, L is halo.

[0179] Non-limiting examples of R (e.g., in Formula (IV), (IVa), or any other formula herein) include -CX y H 3-y , y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I);-CX z H 2-z CX y H 3-y , z is 0, 1, or 2, y is 0, 1, 2, or 3, each X is independently halo (F, Cl, Br, or I), and at least one of z or y is not 0; y H 3-y , y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I); n H 2n+1-z X z , n is 1, 2, 3, or more, z is 1 to 2n+1 (e.g., 1 to 3, 1 to 5, or 1 to 7), and each X is independently halo (F, Cl, Br, or I); n H 2n+1 , n is 1 or 2;-C n H 2n-1 , n is 2, 3, or 4; or -C n H 2n-3 , n is 2, 3, or 4. Still other non-limiting haloalkyl groups include halo-substituted methyl, etc., containing 1, 2, or 3 halo substituents as described herein; halo-substituted ethyl, containing 1, 2, or 3 halo substituents; and β-halo-substituted ethyl, containing 1, 2, or 3 halo substituents (e.g., as described herein).

[0180] Non-limiting examples of L (e.g., for Formula (II), (IIa), (IV), or (IVa)) include H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy (e.g., -OR 1 , R 1 In some embodiments, an optionally substituted amino is -NR 1 R 2 And 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, and each R 1 , R 2 , and R 3 is independently alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR 1 R 2 R 3 And each R 1 , R 2 , and R 3 is independently alkyl.

[0181] In some embodiments, each L or at least one L can include an oxygen atom. In certain embodiments, one or more L can be an optionally substituted alkoxy (e.g., in formula (II), (IIa), (IV), or (IVa)). Non-limiting L substituents include, for example, methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), 1-methoxy-2-methyl-2-propanolate (mmp), 2,2,6,6-tetramethyl-3,5-heptanedionato (THD), acetylacetonate (acac), and -OC(Z a )-CZ a -C(Z a )-O-(β-diketonates, a can be independently H, alkyl, alkenyl, alkynyl, aryl, phenyl, or halo).

[0182] In some embodiments, each L or at least one L can include a nitrogen atom. In certain embodiments, one or more L can be an optionally substituted amino (e.g., in formula (II), (IIa), (IV), or (IVa)) or an optionally substituted bis(trialkylsilyl)amino. Non-limiting L substituents include, for example, dialkylamino; dimethylamino (-NMe2); diethylamino (-NEt2); diethylmethylamino (-NMeEt); -N(t-Bu)-[CHCH3]2-N(t-Bu)-(tbba); bis(trimethylsilyl)amino (-N(SiMe3)2); bis(triethylsilyl)amino (-N(SiEt3)2); 3-(dimethylamino)propyl (dmp); -NR 1 R 2 -C(Z a )2-C(Z a )2-C(Z a ) 2-(dialkylaminopropyl), each Z a , R 1 , and R 2 may be independently H, alkyl, alkenyl, alkynyl, aryl, phenyl, or halo; a )-C(Z a )-N(Z a)-(amidinato), each Z a may be independently H, alkyl, alkenyl, alkynyl, aryl, phenyl, or halo, including N,N'-di-sec-butylacetamidinato [(iPrN)CMe]; -N(Z a )-C(NR 1 R 2 )-N(Z a )-(guanidinate), each Z a , R 1 , and R 2 may be independently H, alkyl, alkenyl, alkynyl, aryl, phenyl, or halo; or -N(Z a )-C(Z a )-C(Z a )-C(Z a )-N(Z a )-(β-diketiminato), each Z a can be independently H, alkyl, alkenyl, alkynyl, aryl, phenyl, or halo.

[0183] In some embodiments, each L or at least one L can include an optionally substituted cyclopentadienyl (Cp) or an optionally substituted aryl. Non-limiting substituents for Cp and aryl include alkyl, alkenyl, alkynyl, aryl, phenyl, or halo, such as alkylated derivatives (e.g., η 5 —C5H4Et) may be mentioned.

[0184] Other ligand-containing precursors can include organolithium compounds such as lithium dimethylamide [LiNMe2] and lithium bis(trimethylsilyl)amide [LiN(SiMe3)2].

[0185] Still other ligand-containing precursors may include aluminum halides, such as aluminum bromide [AlBr3] and aluminum chloride [AlCl3]; organoaluminums, including trialkylaluminums and triarylaluminums, such as trimethylaluminum [AlMe3] and triethylaluminum [AlEt3]; aluminum alkoxides, such as aluminum methoxide [Al(OMe)3] and aluminum i-propoxide [Al(OiPr)3]; tris(dialkylamido)aluminums, such as tris(dimethylamido)aluminum [Al(NMe2)3 or Al2(NMe2)6].

[0186] Still other ligand-containing precursors may include haloalkyl halides or alkyl halides, such as haloalkyl iodides, haloalkyl bromides, haloalkyl chlorides, haloalkyl fluorides, alkyl iodides, alkyl bromides, alkyl chlorides, or alkyl fluorides. In some embodiments, the haloalkyl is -CX y H 3-y , y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I);-CX z H 2-z CX y H 3-y , z is 0, 1, or 2, y is 0, 1, 2, or 3, each X is independently halo (F, Cl, Br, or I), and at least one of z or y is not 0; y H 3-y , y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I); or C n H 2n+1-z X z, n is 1, 2, 3, or more, z is 1 to 2n+1 (e.g., 1 to 3, 1 to 5, or 1 to 7), and each X is independently halo (F, Cl, Br, or I). Still other non-limiting haloalkyl groups include halo-substituted methyl, etc., containing 1, 2, or 3 halo substituents as described herein; halo-substituted ethyl, containing 1, 2, or 3 halo substituents; and β-halo-substituted ethyl, containing 1, 2, or 3 halo substituents (e.g., as described herein). In other embodiments, alkyl is selected from the group consisting of -C n H 2n+1 , n is 1 or 2;-C n H 2n-1 , n is 2, 3, or 4; or -C n H 2n-3 , n is 2, 3, or 4.

[0187] Still other ligand-containing precursors and non-limiting substituents (e.g., R and L) are described herein. For example, any of the substituents M, R, X, or L described herein for (I), (Ia), (III), (IIIa), (V), (Va), (VI), (VII), (VIII), (IX), (X), or (XI) can be used in any of formulas (II), (IIa), (IV), or (IVa).

[0188] Further Precursors As described herein, the films, layers, and methods herein can be used with any useful precursor. The following precursors can be used as metal-containing or ligand-containing precursors:

[0189] In a non-limiting example, the precursor has the formula (V): M a R b L c (V)

[0023] M is a metal or metalloid; each R is independently 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 that reacts with a reverse 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.

[0190] In some embodiments, each ligand in the precursor can be a ligand that reacts with a reverse reactant. In one example, the precursor comprises a structure having formula (V), where each R is independently L. In another example, the precursor comprises a structure having formula (Va): M a L c (Va)

[0023] M is a metal, each L is independently a ligand, ion, or other moiety that reacts with a reverse reactant, and two L's together can optionally form a heterocyclyl group; a≧1, and c≧1. In certain embodiments of Formula (Va), a is 1. In further embodiments, c is 2, 3, or 4.

[0191] For any formula herein, M is a high patterning radiation absorption cross section (e.g., 1×10 7 cm 2M may be a metal having an EUV absorption cross section of 1000 nm / mol or more. In some embodiments, M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), hafnium (Hf), or zirconium (Zr). In further embodiments, in formula (V) or (Va), M is Sn, a is 1, and c is 4. In other embodiments, in formula (V) or (Va), M is Sn, a is 1, and c is 2. In certain embodiments, M is Sn(II) (e.g., in formula (V) or (Va)), thereby providing a precursor that is a Sn(II)-based compound. In other embodiments, M is Sn(IV) (e.g., in formula (V) or (Va)), thereby providing a precursor that is a Sn(IV)-based compound.

[0192] For any formula herein, 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 (e.g., -OR 1 , R 1 In some embodiments, an optionally substituted amino is -NR 1 R 2 And 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, and each R 1 , R 2 , and R 3 is independently alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR 1 R 2R 3 And each R 1 , R 2 , and R 3 is independently alkyl.

[0193] In other embodiments, the formula is -NR 1 R 2 The first L and -NR 1 R 2 Each R 1 and R 2 is independently H or alkyl, or the first L to R 1 and R from the second L 1 taken together with the nitrogen atom and metal atom to which each is attached, form a heterocyclyl group as defined herein. 1 The first L and -OR 1 Each R 1 is independently H or alkyl, or the first L to R 1 and R from the second L 1 together with the oxygen atom and metal atom to which each is attached form a heterocyclyl group, as defined herein.

[0194] In some embodiments, at least one of L or R is an optionally substituted alkyl (e.g., in formula (V) or (Va)). Non-limiting alkyl groups include, for example, C n H 2n+1 where n is 1, 2, 3, or more, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. In various embodiments, L or R has at least one beta hydrogen or beta fluorine. In particular, the precursor can be tetramethyltin (SnMe4), tetraethyltin (SnEt4), t-butyl tellurium hydride (Te(t-Bu)(H)), dimethyltellurium (TeMe2), di(t-butyl)tellurium (Te(t-Bu)2), or di(isopropyl)tellurium (Te(i-Pr)2).

[0195] In some embodiments, each L or at least one L is halo (e.g., in formula (V) or (Va)). In particular, the precursor can be a metal halide. Non-limiting metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0196] In some embodiments, each L or at least one L can include a nitrogen atom. In certain embodiments, one or more L can be an optionally substituted amino or an optionally substituted bis(trialkylsilyl)amino (e.g., in formula (V) or (Va)). Non-limiting L substituents can include, for example, -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)-(tbba), -N(SiMe3)2, and -N(SiEt3)2. Non-limiting precursors can include, for example, Sn(NMe2)4, Sn(NEt2)4, 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, Sb(NMe2)3, Sn(tbba), Sn[N(SiMe3)2]2, or Bi[N(SiMe3)2]3.

[0197] In some embodiments, each L or at least one L can include a silicon atom. In certain embodiments, one or more L can be an optionally substituted trialkylsilyl or an optionally substituted bis(trialkylsilyl)amino (e.g., in formula (V) or (Va)). Non-limiting L substituents can include, for example, -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2. Non-limiting precursors can include, for example, Sn[N(SiMe3)2]2, bis(trimethylsilyl)tellurium (Te(SiMe3)2), bis(triethylsilyl)tellurium (Te(SiEt3)2), or Bi[N(SiMe3)2]3.

[0198] In some embodiments, each L or at least one L can include an oxygen atom. In certain embodiments, one or more L can be an optionally substituted alkoxy (e.g., in formula (V) or (Va)). Non-limiting L substituents include, for example, methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), and -O=C(CH3)-CH=C(CH3)-O-(acac). Non-limiting precursors include, for example, Sn(t-BuO)4, Sn(n-Bu)(t-BuO)3, or Sn(acac)2.

[0199] In some cases, the precursor has the following formula (VI): MX n (VI) and a metal halide having the formula: Depending on the selection of M, M is a metal, X is halo, and n is 2 to 4. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0200] Another non-limiting precursor is represented by formula (VII): MR n (VII)

[0023] M is a metal and 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), where each R is independently alkyl), or optionally substituted trialkylsilyl (e.g., -SiR3, where each R is independently alkyl), and n is 2-4, depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. The alkyl group can be selected from the group consisting of CnH 2n+1 where n is 1, 2, 3, or more. Exemplary organometallic agents include SnMe4, SnEt4, TeR n, RTeR, t-butyl tellurium hydride (Te(t-Bu)(H)), dimethyltellurium (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.

[0201] Another non-limiting precursor is represented by the following formula (VIII): ML n (VIII) and a capping agent having the formula: M is a metal and each L is independently an optionally substituted alkyl, amino (e.g., -NR 1 R 2 , R 1 and R 2 Each of may be H or alkyl as any described herein), alkoxy (e.g., -OR, where R is alkyl as any described herein), halo, or other organic substituents, and depending on the selection of M, n is 2-4. 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 substituents (e.g., acetylacetone or N 2 ,N 3 -di-tertbutyl-butane-2,3-diamino). Non-limiting capping agents include SnCl4, SnI4, Sn(NR2)4, where each R is independently methyl or ethyl, or Sn(t-BuO)4. In some embodiments, multiple types of ligands are present.

[0202] The precursor has the following formula (IX): R n MX m (IX) and a hydrocarbyl substituted capping agent having the formula: M is a metal and R is a C with beta hydrogen 2-10 R is alkyl or substituted alkyl, and X is a suitable leaving group for reaction with the hydroxyl group of the exposed hydroxyl group. In various embodiments, n=1-3, and m=4-n, 3-n, or 2-n, as long as 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 derivatives thereof with 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-pentyl ... Examples of suitable tin ions include tris(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).

[0203] In various embodiments, the metal-containing precursor comprises at least one alkyl group on each metal atom capable of undergoing a gas phase reaction, and other ligands or ions coordinated to the metal atom can be displaced by a counter reactant. Thus, another non-limiting metal-containing precursor has the formula (X): M a R b L c (X) and M is a metal, R is an optionally substituted alkyl, L is a ligand, ion, or other moiety that reacts with a reverse reactant, and 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 , R 1 and R 2 Each of may be H or alkyl as described herein), alkoxy (e.g., -OR, where R is alkyl as described herein), or halo (e.g., F, Cl, Br, or I). Exemplary agents include SnMe3Cl, SnMe2Cl2, SnMeCl3, SnMe(NMe2)3, SnMe2(NMe2)2, and the like.

[0204] In other embodiments, the non-limiting precursor has formula (XI): M a L c (XI) and an organometallic agent having the formula: M is a metal and L is a ligand, ion, or other moiety that reacts with the counter-reactant, where 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 a reactive moiety, ligand, or ion (e.g., L in the formulas herein) so as to link at least two metal atoms via a chemical bond.

[0205] In any embodiment herein, R is optionally substituted alkyl (e.g., C 1-10 In one embodiment, the alkyl can be substituted with one or more halo (e.g., halo-substituted C , including one, two, three, four, or more halo, such as F, Cl, Br, or I). 1-10 Exemplary R substituents include C alkyl, preferably with n≧3. n H 2n+1 , and C with 2n+1≦x≦1 n F x H( 2n+1-x 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.

[0206] In any embodiment herein, L is an M-OH moiety, such as amino (e.g., -NR 1 R 2 , R 1 and R 2 may be any moiety that is readily displaced by a reverse reactant to produce a moiety selected from the group consisting of: alkyl (e.g., -OR, where R is alkyl as any of those described herein), alkoxy (e.g., -OR, where R is alkyl as any of those described herein), carboxylate, halo (e.g., F, Cl, Br, or I), and mixtures thereof.

[0207] 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 replaced by C 2-12Alkenyl, 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 dinitrogen chelates (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), and Ak is an optionally substituted C 1-6Non-limiting examples of tin precursors include SnF2, SnH4, SnBr4, SnCl4, SnI4, tetramethyltin (SnMe4), tetraethyltin (SnEt4), trimethyltin chloride (SnMe3Cl), dimethyltin dichloride (SnMe2Cl2), methyltin trichloride (SnMeCl3), tetraallyltin, tetravinyltin, hexaphenylditin(IV) (Ph3Sn-SnPh3, where Ph is phenyl), dibutyltin, tetraphenyl ... Diphenyltin (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), Sn(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-diazastanolidine-2-ylidene), or bis[bis(trimethylsilyl)amino]tin (Sn[N(SiMe3)2]2).

[0208] Exemplary organometallic agents include SnMeCl3, (N 2 ,N 3-di-t-butyl-butane-2,3-diamide)tin(II) (Sn(tbba)), bis(bis(trimethylsilyl)amide)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), sec-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 similar alkyl(tris)(t-butoxy)tin compounds such as t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO)3). In some embodiments, the organometallic agent is partially fluorinated.

[0209] Lithography Process EUV lithography utilizes an EUV resist, which can be a polymer-based chemically amplified resist delivered by liquid-based spin-on techniques, or a metal oxide-based resist delivered by dry vapor deposition techniques. Such an EUV resist can include any EUV-sensitive film or material described herein. Lithography methods can include, for example, patterning the resist by exposing the EUV resist to EUV radiation to form a photopattern, and subsequently developing the pattern by removing portions of the resist according to the photopattern to form a mask.

[0210] It should also be understood that the present disclosure relates to lithographic patterning techniques and materials exemplified by EUV lithography, but is also applicable to other next-generation lithography techniques. In addition to EUV, which includes 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), which generally refers to the use of 248 nm or 193 nm excimer laser sources, X-ray, which formally includes EUV at the lower energy range of the X-ray range, and e-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 including a network of metal oxide bonds, which may include other non-metallic and non-oxygen groups) film as an imaging / photoresist (PR) layer on the surface of the substrate. The specific method may depend on the particular materials and applications used in the semiconductor substrate and the final semiconductor device. Thus, the methods described in this application are merely exemplary of methods and materials that can be used with current technology.

[0211] Direct photopatternable EUV resists may be composed of or include metals and / or metal oxides mixed within an organic component. Metals / metal oxides are very promising in that they can enhance EUV photon adsorption, generate secondary electrons, and / or exhibit increased etch selectivity to the underlying film stack and device layers. To date, these resists have been developed using a wet (solvent) approach, which requires the wafer to be moved to a track where it is exposed to a developing solvent, dried, and baked. Wet development not only limits productivity, but can also lead to line collapse due to surface tension effects during evaporation of the solvent between fine features.

[0212] Dry development techniques have been proposed to overcome these issues by eliminating substrate delamination and interface failure. Dry development has its own challenges, including etch selectivity between unexposed and EUV-exposed resist materials, which can lead to higher dose-to-size requirements for effective resist exposure when compared to wet development. Suboptimal selectivity can also cause PR corner rounding due to longer exposure under etching gases, which can increase line CD variations in the following transfer etch step. Additional processes used during lithography are described in detail below.

[0213] Deposition processes, including dry deposition As mentioned above, the present disclosure provides methods for producing imaging layers on semiconductor substrates, which can be patterned using EUV or other next generation lithography techniques. Methods include methods in which a polymerized organometallic material is generated in vapor and deposited on a substrate. In some embodiments, the dry deposition can use any useful metal-containing precursor (e.g., metal halides, capping agents, or organometallic agents described herein). In other embodiments, spin-on formulations can be used. The deposition process can include applying an EUV-sensitive material as a resist film and / or as a capping layer on the resist film. Exemplary EUV-sensitive materials are described herein.

[0214] The present technique includes a method for depositing an EUV sensitive film on a substrate, such film being operable as a resist for subsequent EUV lithography and processing. Additionally, a secondary EUV sensitive film can be deposited over an underlying primary EUV sensitive film. In one example, the secondary film constitutes a capping layer and the primary film constitutes an imaging layer.

[0215] Such EUV-sensitive films include materials that upon exposure to EUV undergo changes such as loss of bulky pendant ligands bonded to metal atoms in a low density M-OH rich material, allowing crosslinking to a higher density MOM-bonded metal oxide material. In other embodiments, EUV exposure results in further crosslinking between ligands bonded to metal atoms, thereby providing a higher density MLM-bonded organometallic material, where L is a ligand. In yet other embodiments, EUV exposure results in loss of ligands, providing a M-OH material that can be removed by a positive tone developer.

[0216] EUV patterning creates regions of the film 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 in either the exposed or unexposed regions. In some embodiments, the unexposed film has a hydrophobic surface and the exposed film has a hydrophilic surface under the conditions under which such subsequent processing is carried out (it is recognized that the hydrophilic nature of the exposed and unexposed regions is interrelated). For example, material removal can be achieved by exploiting differences in the chemical composition, density, and crosslinking of the film. Removal can be by wet or dry processing, as further described herein.

[0217] The thickness of the EUV patternable film formed on the surface of the substrate may vary according to the surface characteristics, the materials used, and the processing conditions. In various embodiments, the film thickness may range from about 0.5 to about 100 nm. Preferably, the film has a thickness sufficient to absorb a majority of the EUV light under the conditions of EUV patterning. For example, the overall absorption of the resist film may be 30% or less (e.g., 10% or less, or 5% or less) such that the resist material at the bottom of the resist film is fully exposed. In some embodiments, the film thickness is 10 to 20 nm. Without limiting the mechanism, function, or utility of the present disclosure, it is believed that unlike wet spin coating processes of the art, the processes of the present disclosure have fewer limitations on the surface adhesion properties of the substrate and therefore may be applied to a wider variety of substrates. Additionally, as discussed above, the deposited film may conform closely to surface features, providing advantages in forming a mask over a substrate, such as a substrate having underlying features, without "filling" or planarizing such features.

[0218] The film (e.g., imaging layer) or capping layer may be comprised of a metal oxide layer deposited in any useful manner. Such metal oxide layers may be deposited or applied by using any EUV-sensitive material described herein, such as a metal-containing precursor (e.g., metal halide, capping agent, or organometallic agent) in combination with an optional ligand-containing precursor. In an exemplary process, a polymerized organometallic material is formed in the gas 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 film, an adhesion layer, or a capping layer.

[0219] Optionally, the metal oxide layer can include a hydroxyl-terminated metal oxide layer, which can be deposited by using a capping agent (e.g., any described herein) with an oxygen-containing reverse 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 film, and / or between a photoresist layer and a capping layer.

[0220] Exemplary deposition techniques (e.g., for films or capping layers) include any 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 CVD components, such as discontinuous ALD-like processes in which the metal-containing precursor, ligand-containing precursor, and counter-reactant are separated in either time or space.

[0221] Further description of precursors and methods for their deposition as EUV photoresist films applicable to the present disclosure can be found in International Application No. PCT / US19 / 31618, entitled METHODS FOR MAKING EUV PATTERNABLE HARD MASKS, published as International Publication No. WO2019 / 217749, filed May 9, 2019. The thin films can include optional materials in addition to the metal-containing precursor, the ligand-containing precursor, and the back reactant to modify the chemical or physical properties of the film, such as modifying the film's sensitivity to EUV or enhancing etch resistance. Such optional materials may be introduced, such as by doping during gas-phase formation before deposition on the substrate, after deposition of the film, or both. In some embodiments, a mild remote H2 plasma can be introduced to, for example, replace some Sn-L bonds with Sn-H, which can increase the reactivity of the resist under EUV.

[0222] In general, the method can include mixing a vapor flow of an organometallic precursor (e.g., a metal-containing precursor such as an organometallic agent) with an optional vapor flow of a ligand-containing precursor and an optional vapor flow of a reverse reactant to form a polymerized organometallic material, and depositing the organometallic material onto a surface of a semiconductor substrate. In some embodiments, the metal-containing precursor can be mixed with the optional ligand-containing precursor and the optional reverse reactant to form the polymerized organometallic material. As will be appreciated by those skilled in the art, the mixing and deposition aspects of the process can be simultaneous in a substantially continuous process.

[0223] In an exemplary sequential CVD process, two or more gas streams of a source of a metal-containing precursor, an optional ligand-containing precursor, and an optional back reactant are introduced in separate inlet paths into a deposition chamber of a CVD apparatus where they mix and react in the gas phase to form an aggregate polymeric material or film on a substrate (e.g., via metal-oxygen-metal bond formation). The gas streams can be introduced, for example, using separate injection inlets or a dual plenum showerhead. The apparatus is configured such that the flows of the metal-containing precursor, the optional ligand-containing precursor, and the optional back reactant are mixed in the chamber, thereby allowing the metal-containing precursor, the optional ligand-containing precursor, and the optional back reactant to react and form a polymerized organometallic material or film (e.g., a metal oxide coating or an aggregate polymeric material via metal-oxygen-metal bond formation, etc.).

[0224] To deposit metal oxides, the CVD process is typically carried out at reduced pressure, such as 0.1-10 Torr. In some embodiments, the process is carried out at a pressure of 1-2 Torr. The temperature of the substrate is preferably lower than the temperature of the reactant stream. For example, the substrate temperature can be from 0 to 250° C., or from ambient temperature (e.g., 23° C.) to 150° C.

[0225] To deposit the coagulated polymeric material, CVD processes are generally performed at reduced pressures, such as 10 mTorr to 10 Torr. In some embodiments, the process is 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 can be 0 to 250°C, or ambient temperature (e.g., 23°C) to 150°C. In various processes, deposition of the polymerized organometallic material onto the substrate occurs at a rate inversely proportional to the surface temperature. Without limiting the mechanism, function, or utility of the present technology, it is believed that the products from such gas-phase reactions become heavier in molecular weight as metal atoms are crosslinked by ligand-containing precursors and / or back reactants, and are then condensed or, in some cases, deposited onto the substrate.

[0226] A potential advantage of using dry deposition methods is that the composition of the film can be easily adjusted as it grows. In a CVD process, this can be accomplished by altering the relative flows of the metal-containing precursor and the ligand-containing precursor during deposition. Deposition may be carried out at temperatures between 30 and 200 °C and pressures between 0.01 and 100 Torr, more commonly around 0.1 to 10 Torr.

[0227] Films (e.g., metal oxide coatings or aggregated polymeric materials, such as via metal-oxygen-metal bond formation) can also be deposited by ALD processes. For example, a metal-containing precursor, an optional ligand-containing precursor, and an optional back reactant are introduced at separate times representing ALD cycles. The metal-containing precursor and the optional ligand-containing precursor react on the surface to form up to a monolayer of material at a time in each cycle. This can allow for excellent control over the uniformity of film thickness across the surface. ALD processes are generally performed at reduced pressures, such as 0.1 to 10 Torr. In some embodiments, the process is performed at 1 to 2 Torr. The substrate temperature can be 0 to 250° C., or ambient (e.g., 23° C.) to 150° C. The process can be a thermal process, or preferably, a plasma-assisted deposition.

[0228] Any of the deposition methods herein can be modified to allow the use of two or more different metal-containing 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 flows of various volatile metal-containing precursors can provide mixed metal layers, such as using a metal alkoxide precursor with a first metal (e.g., Sn) and a silyl-based precursor with a different second metal (e.g., Te).

[0229] Any of the deposition methods herein can also be modified to allow the use of two or more different ligand-containing precursors. In one embodiment, the ligand-containing precursors can provide different binding ligands to the metal center. In one non-limiting example, the alternating flow of various ligand-containing precursors can provide layers with different ligand contents, such as in a gradient membrane.

[0230] Additionally, any of the deposition methods herein can be modified to provide one or more layers within the film or capping layer. In one example, different metal-containing and / or ligand-containing 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 density of metal-ligand bonds, different metal-to-carbon ratio, different halogen content, or different binding ligands, as provided by adjusting or modifying the metal-containing and / or ligand-containing precursors).

[0231] The processes herein can be used to achieve surface modification. In some iterations, vapors of a metal-containing precursor can be passed over the wafer. The wafer can be heated to provide thermal energy for the reaction to proceed. In some iterations, the heating can be about 50-250°C. In some cases, pulses of metal-containing precursor and / or ligand-containing precursor can be used, separated by pump and / or purging steps. In one example, the ligand-containing precursor can be pulsed between pulses of precursor to provide ALD or ALD-like growth. In other cases, both the metal-containing precursor and the ligand-containing precursor can be flowed simultaneously. Examples of elements useful for surface modification include I, F, Sn, Bi, Sb, Te, and oxides or alloys of these compounds.

[0232] The processes herein can be used to deposit thin metal oxides or metals by ALD or CVD. Examples include SnOx, BiOx, and Te. Following deposition, the films can be modified with M, as described elsewhere herein. a R b L c The surface may be capped with a haloalkyl- or alkyl-substituted precursor in the form of a tetrakis(dimethylamino)tin. A back reactant can be used to better remove the ligands, and multiple cycles can be repeated to ensure complete saturation of the substrate surface. The surface is then ready for depositing an EUV-sensitive film. One possible method is to generate a thin film of SnOx. Possible chemistries include growth of SnO2 by circulating a back reactant such as tetrakis(dimethylamino)tin and water or O2 plasma. After growth, a capping agent can be used. For example, vapor of isopropyltris(dimethylamino)tin may be flowed over the surface.

[0233] The deposition process can be used on any useful surface. As referred to herein, a "surface" is a surface on which the film of the present technology is deposited or is exposed to EUV during processing. Such a surface can be on a substrate (e.g., on which a film is deposited), on a film (e.g., on which a capping layer is deposited), or on a capping layer.

[0234] Any useful substrate can be used, including any material structure suitable for lithographic processing, particularly for the manufacture 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 having irregular surface topography ("underlying topographical features") are formed.

[0235] Such underlying topographical features may include areas where material has been removed (e.g., by etching) or where material has been added (e.g., by deposition) during processing prior to performing the method of the present technology. Such pre-processing may include other processing methods of the present technology or in an iterative process, 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 method of the present technology is believed to provide advantages over methods known in the art for depositing photolithographic films onto the surface of a substrate using spin casting methods. Such advantages may derive from the conformity of the film of the present technology to the underlying features without "filling" or planarizing such features, and the ability to deposit films onto a wide variety of material surfaces.

[0236] In some embodiments, a next wafer can be prepared having a substrate surface of the desired material, with the top material being the layer to which the resist pattern will be transferred. The choice of material can vary depending on the integration, but in general it is desirable to select a material that can be etched with high selectivity to (i.e., much faster than) the EUV resist or imaging layer. Suitable substrate materials include various carbon-based films (e.g., ashable hardmasks (AHMs)), silicon-based films (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, or any other film (typically a sacrificial film) applied to facilitate the patterning process.

[0237] In some embodiments, the substrate is a hard mask used in the lithographic etching of the underlying semiconductor material. The hard mask may be made 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 be made of a SnO2, such as SnO2, HfO2, ZrO2, and Al2O3. x In various embodiments, the layer can be 1 to 100 nm thick, or 2 to 10 nm thick.

[0238] In some non-limiting embodiments, the substrate includes an underlayer. The underlayer can be deposited on a hard mask or other layer, and generally underlies the imaging layer (or film) described herein. The underlayer can be used to improve the sensitivity of the PR, increase the EUV absorption rate, and / or increase the patterning performance of the PR. If there are device features present on the substrate to be patterned that form significant topography, another important function of the underlayer is that it can overcoat and planarize the existing topography, so that subsequent patterning steps can be performed on a flat surface with all areas of the pattern in focus. In such applications, the underlayer (or at least one of the underlayers) can be applied using spin-coating techniques. If the PR material used has a significant inorganic component, e.g., exhibits a predominantly metal oxide framework, the underlayer can advantageously be a carbon-based film applied by either spin-coating or a dry vacuum-based deposition process. The layers can include a variety of ashable hardmask (AHM) films having carbon-based and hydrogen-based compositions, and can be doped with additional elements such as tungsten, boron, nitrogen, or fluorine.

[0239] In some embodiments, a surface activation operation can be used to activate a surface (e.g., of a substrate and / or film) for future operations. For example, SiO x For surfaces, water or oxygen / hydrogen plasma can be used to form hydroxyl groups on the surface. For carbon- or hydrocarbon-based surfaces, various treatments (e.g., water, hydrogen / oxygen, CO2 plasma, or ozone treatments) can be used to form carboxylic acid and / or hydroxyl groups. Such approaches have proven important in improving adhesion of resist features to substrates that may peel or lift off in some cases during handling or in solvents during development.

[0240] Adhesion can also be enhanced by inducing roughness in the surface to increase the surface area available for interaction and to directly improve mechanical adhesion. For example, a sputtering process using Ar or other non-reactive ion bombardment can be used first to result in 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. On carbon, a combination approach can be used in which a chemically reactive oxygen-containing plasma such as CO2, O2, or H2O (or a mixture of H2 and O2) can be used to etch away a thin layer of the film with localized inhomogeneities and simultaneously terminate with -OH, -OOH, or -COOH groups. This approach can be performed with or without bias. In conjunction with the surface modification strategies described above, this approach can serve the dual purpose of roughening and chemical activation of the substrate surface for direct adhesion to inorganic metal oxide-based resists or as an intermediate surface modification for further functionalization.

[0241] In various embodiments, the surface (e.g., of a substrate and / or film) includes exposed hydroxyl groups on its surface. In general, the surface can be any surface that includes, or has been treated to provide, an exposed hydroxyl surface. Such hydroxyl groups can 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 film can be treated to provide exposed hydroxyl groups, over which a capping layer can be applied. In various embodiments, the hydroxyl-terminated metal oxide layer has a thickness of 0.1 to 20 nm, or 0.2 to 10 nm, or 0.5 to 5 nm.

[0242] EUV exposure process EUV exposure of the film can provide EUV-exposed regions with activated reactive centers containing a metal atom (M) resulting from an EUV-mediated cleavage event. Such reactive centers can include dangling metal bonds, M-H groups, cleaved M-ligand groups, dimerized M-M bonds, or M-O-M bridges. In other embodiments, EUV exposure provides cross-linked organic moieties by photopolymerizing ligands within the film, or EUV exposure releases gaseous by-products resulting from photolysis of bonds within the ligands.

[0243] The EUV exposure can have a wavelength in the range of about 10 to 20 nm, for example, 10 to 15 nm, for example, 13.5 nm, in a vacuum atmosphere. In particular, the patterning can provide EUV exposed areas and EUV non-exposed areas to form a pattern.

[0244] The present technology can include patterning using EUV, as well as DUV or e-beam. In such patterning, radiation is focused on one or more areas of the imaging layer. Exposure is typically performed such that the imaging layer film includes one or more areas that are not exposed to radiation. The resulting imaging layer can include multiple exposed and unexposed areas, forming a pattern that coincides with the formation of transistors or other features of a semiconductor device that are formed by adding or removing material from the substrate in subsequent processing of the substrate. EUV, DUV, and e-beam radiation methods and equipment useful herein include methods and equipment known in the art.

[0245] In some EUV lithography techniques, an organic hardmask (e.g., a PECVD amorphous hydrogenated carbon ashable hardmask) is patterned using conventional photoresist processes. During photoresist exposure, EUV radiation is absorbed by the resist and the underlying substrate, generating high-energy photoelectrons (e.g., about 100 eV) and then a cascade of lower-energy secondary electrons (e.g., about 10 eV) that diffuse laterally by a few nanometers. These electrons increase the extent of chemical reactions in the resist and increase its EUV dose sensitivity. However, an essentially random secondary electron pattern is superimposed on the optical image. This undesirable secondary electron exposure results in loss of resolution, observable line edge roughness (LER), and linewidth variations in the patterned resist. These defects are replicated in the material being patterned during the subsequent pattern-transfer etch.

[0246] 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 significantly improved EUV lithography (EUVL) performance, e.g., reduced line edge roughness.

[0247] 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 film of a metal-containing film, such as a photosensitive metal salt or metal-containing organic compound (organometallic compound), that has strong absorption in the EUV (e.g., at wavelengths on the order of 10-20 nm), for example at the wavelength of an EUVL light source (e.g., 13.5 nm = 91.8 eV). This film photodecomposes upon EUV exposure and forms a metal mask that is a pattern transfer layer during subsequent etching (e.g., in a conductor etch tool such as a Lam 2300® Kiyo®).

[0248] Following deposition, the EUV patternable thin film is patterned by exposure to a beam of EUV light, typically under a relatively high vacuum. For EUV exposure, the metal-containing film may be deposited in a chamber integrated with 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 so as not to react prior to exposure. Integration with the lithography tool is facilitated by the fact that EUVL also requires a significantly reduced pressure, given the strong optical absorption of incident photons by ambient gases such as H2O, O2, etc. In other embodiments, photosensitive metal film deposition and EUV exposure can occur in the same chamber.

[0249] Development process, including dry development The EUV exposed or unexposed regions, as well as the capping layer, can be removed by any useful development process. In one embodiment, the EUV exposed regions can have activated reactive centers, such as dangling metal bonds, MH groups, or dimerized MM bonds. In certain embodiments, the MH groups can be selectively removed by using one or more dry development processes (e.g., halide chemistries). In other embodiments, the MM bonds can be selectively removed by using a wet development process, for example, using hot ethanol and water to form soluble M(OH) n It is possible to selectively remove the EUV-exposed regions by providing groups. In yet other embodiments, the EUV-exposed regions are removed by using wet development (e.g., by using a positive tone developer). In some embodiments, the EUV-unexposed regions are removed by using dry development.

[0250] Dry development processes can also include the use of halides, such as HCl-based or HBr-based processes. While this disclosure is not limited to a particular theory of operation or mechanism, it is understood that the approach leverages the chemical reactivity of dry-deposited EUV photoresist films with clean 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 for chamber cleaning, backside cleaning, bevel cleaning, and PR development. 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), but plasma can also be used to further accelerate or enhance the reactivity.

[0251] Plasma processes include transformer coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP) using equipment and techniques known in the art. For example, the process can be performed at a pressure of >0.5 mTorr (e.g., 1-100 mTorr, etc.) and a power level of <1000 W (e.g., <500 W). The temperature can be 30-300° C. (e.g., 30-120° C.) for 1-3000 seconds (e.g., 10 seconds to 600 seconds) with a flow rate of 100-1000 standard cubic centimeters per minute (sccm), e.g., about 500 sccm.

[0252] When the halide reactant flow is hydrogen gas and halide gas, remote plasma / UV radiation is used to generate radicals from H2 and Cl2 and / or Br2, and the hydrogen and halide radicals are flowed into the reaction chamber and contacted with the patterned EUV photoresist on the substrate layer of the wafer. Suitable plasma powers can range from 100-500 W, without bias. These conditions are suitable for some processing reactors, e.g., Kiyo etch tools available from Lam Research, Inc., Fremont, Calif., but it should be understood that a wider range of process conditions can be used depending on the capabilities of the processing reactor.

[0253] In a thermal development process, the substrate is exposed to a dry development chemical (e.g., Lewis acid) in a vacuum chamber (e.g., oven). A suitable chamber can 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 chamber interior can be coated with a corrosion resistant film, such as an organic polymer or inorganic coating. One such coating is polytetrafluoroethylene ((PTFE), e.g., Teflon™). Such materials can be used in the thermal processes of the present disclosure without the risk of removal by plasma exposure.

[0254] The process conditions for dry development can be about 10 seconds to 1 minute without plasma, reactant flow rate of 100 to 500 sccm (e.g., 500 sccm HBr or HCl), temperature of -10 to 120°C (e.g., -10°C), and pressure of 1 to 500 mTorr (e.g., 300 mTorr), depending on the photoresist film and capping layer and their composition and properties.

[0255] In various embodiments, the methods of the present disclosure combine all dry steps of film deposition, vapor deposition formation, (EUV) lithography photopatterning, and dry development. In such a process, the substrate can go directly to a dry development / etch chamber following photopatterning in an EUV scanner. Such a process can avoid the material and production costs associated with wet development. Dry processes also offer more tunability and can give additional CD control and / or scum removal.

[0256] In various embodiments, EUV photoresists containing some amount of metal, metal oxide, and organic components can be dry developed by thermal, plasma (including possible photoactivated plasma such as lamp heating or UV lamp heating), or mixed thermal and plasma methods while flowing a dry development gas containing a compound of 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 where the RxZy species selectively removes the exposed material and leaves the unexposed counterpart as a mask. In some embodiments, the exposed portions of the organotin oxide-based photoresist film are removed by dry development according to the present disclosure. Positive tone dry development can be achieved by selective dry development (removal) of the EUV exposed areas exposed to a flow containing hydrogen halide or hydrogen and halides (including HCl and / or HBr) without applying plasma, or a flow of H2 and Cl2 and / or Br2 using UV radiation generated from a remote plasma or plasma to generate radicals.

[0257] Wet development methods can also be used. In certain embodiments, such wet development methods are used to remove the EUV-exposed regions to provide a positive photoresist or a negative resist. In some embodiments, the wet development includes a neutral developer (e.g., a pH-neutral developer such as water) or a peroxide-containing developer (e.g., containing hydrogen peroxide, H2O2). Exemplary non-limiting wet development methods can include the use of a base in an alkaline developer (e.g., an aqueous alkaline developer), such as one that includes ammonium, e.g., 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, organic amines, e.g., mono-, di-, and tri-organic amines (e.g., diethylamine, diethylamine, ethylenediamine, triethylenetetramine), or alkanolamines, e.g., monoethanolamine, diethanolamine, triethanolamine, or diethyleneglycolamine. In other embodiments, the alkaline developer comprises a nitrogen-containing base, such as a compound represented by the 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- and R N1 , R N2 , R N3 , and R N4 Each of X is independently an organic substituent (e.g., an optionally substituted alkyl or any of those described herein), or two or more organic substituents which can be linked together; N1- OH - , F - , Cl - , Br - , I -or other quaternary ammonium cation species known in the art. These bases may also include heterocyclyl nitrogen compounds known in the art, some of which are described herein. Non-limiting combinations include water and a basic developer.

[0258] Other development methodologies can include the use of acids in 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)), as well as combinations thereof. Non-limiting combinations include water and acidic developers.

[0259] In certain embodiments, the positive tone developer is an aqueous alkaline developer (e.g., comprising NH4OH, TMAH, TEAH, TPAH, or TBAH). In other embodiments, the negative tone 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 combinations thereof).

[0260] Any of the developers herein may contain one or more surfactants. The surfactants may contain positive, negative, or neutral charges and may be selected from the group consisting of fluorinated or non-fluorinated surfactants. Non-limiting surfactants include quaternary ammonium salts, ammonium perfluorooctanoate salts, ammonium perfluorononanoate salts, fluorosurfactants, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, alkylbenzene sulfonate, sodium sulfosuccinate, and sodium lauryl sulfate.

[0261] Wet development can include any useful process, including immersion development, puddle development, and spray development. After or during any of these processes, the substrate can be spun to remove the dissolved portions of the film while simultaneously drying the film.

[0262] The development process can include both wet and dry development processes. Such a process can include an initial wet development followed by a later dry development, or vice versa. Development can also be performed in cycles where multiple wet development processes are used, or multiple dry development processes are used, or multiple wet and dry development processes are employed.

[0263] Post-application process The methods herein can include any useful post-application process, as described below.

[0264] In the backside and bevel cleaning process, the vapor and / or plasma can be confined to specific areas of the wafer to ensure that only the backside and bevel are removed without degrading the film on the front side of the wafer. The dry-deposited EUV photoresist film that is removed is generally composed of Sn, O, and C, but the same cleaning approach can be extended to films of other metal oxide resists and materials. In addition, this approach can also be used for film strip and PR rework.

[0265] Suitable process conditions for dry bevel edge and backside cleaning may be reactant flow rates of 100-500 sccm (e.g., 500 sccm HCl, HBr, or H2 and Cl2 or Br2, BCl3 or H2), temperatures of -10 to 120°C (e.g., 20°C), pressures of 20 to 500 mTorr (e.g., 300 mTorr), plasma powers of 0 to 500 W at high frequency (e.g., 13.56 MHz), for times of about 10 to 20 seconds depending on the photoresist film and composition and properties. These conditions are suitable for some processing reactors, e.g., Kiyo etch tools available from Lam Research, Inc., Fremont, Calif., but it should be understood that a wider range of process conditions may be used depending on the capabilities of the processing reactor.

[0266] Photolithography processes typically involve one or more bake steps to promote the chemical reactions necessary to produce chemical contrast between exposed and unexposed areas of the photoresist. For high volume manufacturing (HVM), such bake steps are typically performed on a track where the wafer is baked on a hotplate at a preset temperature under ambient air or possibly N2 flow. More careful control of the bake atmosphere during these bake steps, as well as the introduction of additional reactive gas components into the atmosphere, can help to further reduce dose requirements and / or improve pattern fidelity.

[0267] 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)) and / or exposure (e.g., post-exposure bake (PEB)) and / or development (e.g., post-develop bake (PDB)) can increase the difference in material properties between exposed and unexposed photoresists, thus reducing dose-to-size (DtS), improving PR profile, and improving line edge and width roughness (LER / LWR) after subsequent dry development. Such treatments can involve thermal processes that control temperature, gas atmosphere, and moisture, resulting in improved dry development performance in subsequent processing. In some cases, remote plasma may be used.

[0268] For post-application treatments (e.g., PAB), thermal processes that control temperature, gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, NO, NO, Ar, He, or mixtures thereof) or vacuum, and moisture can be used after deposition and before exposure to change the composition of the unexposed metal and / or metal oxide photoresist. This change can increase the EUV sensitivity of the material, thus achieving reduced dose-to-size and edge roughness after exposure and dry development.

[0269] For post-exposure treatment (e.g., incubation or PEB), a thermal process that controls temperature, gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, NO, NO, Ar, He, or mixtures thereof) or under vacuum, and moisture can be used to change the composition of both the unexposed and exposed photoresist. This change can increase the difference in composition / material properties between the unexposed and exposed photoresist, and the difference in etch rate of the dry development etch gas between the unexposed and exposed photoresist. Thereby, higher etch selectivity can be achieved. Improved selectivity can result in a more square PR profile with improved surface roughness and / or less photoresist residue / scum. In certain embodiments, PEB can be performed in air and in the optional presence of moisture and CO2.

[0270] For post-development treatments (e.g., post-develop bake or PDB), a thermal process that controls temperature, gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, NO, Ar, He, or mixtures thereof) or under vacuum (e.g., using UV), and moisture can be used to change the composition of the unexposed photoresist. In certain embodiments, the conditions also include the use of plasma (e.g., including O2, O3, Ar, He, or mixtures thereof). This change can increase the hardness of the material, which can be beneficial if the film is used as a resist mask in etching the underlying substrate.

[0271] In these cases, in alternative embodiments, the thermal process can be replaced with a remote plasma process to increase the reactive species, lowering the energy barrier to the reaction and increasing productivity. Remote plasma can generate more reactive radicals, thus lowering the reaction temperature / time for the process, leading to increased productivity.

[0272] Thus, one or more processes can be applied to modify the photoresist itself, increasing the selectivity of dry development. This thermal or radical modification can increase the contrast between the unexposed and exposed materials, and thus the selectivity of the subsequent dry development step. The resulting difference between the material properties of the unexposed and exposed materials can be tuned by adjusting process conditions, including temperature, gas flow, moisture, pressure, and / or RF power. The large process latitude enabled by dry development, not limited by the solubility of materials in wet developer solvents, allows for the application of more aggressive conditions, further increasing the achievable material contrast. The resulting high material contrast feeds back into a wider process window for dry development, thus allowing for increased productivity, lower costs, and better defectivity performance.

[0273] A practical limitation of wet developed resist films is the temperature bake limit. Because wet development relies on the solubility of the materials, heating to, for example, 220°C or higher can significantly increase the degree of crosslinking in both exposed and unexposed regions of the metal-containing PR film, rendering both insoluble in the wet development solvent and thus the film no longer reliably wet developable. For dry developed resist films, where the etch rate difference (i.e., selectivity) between exposed and unexposed regions of the PR depends on the removal of only the exposed or unexposed portions of the resist, the processing temperature in PAB, PEB, or PDB can be varied over a much wider window to adjust and optimize the treatment process, for example, from about 90-250°C, e.g., 90-190°C for PAB, and from about 170-250°C or higher, e.g., 190-240°C for PEB and / or PDB. It has been found that reduced etch rates and greater etch selectivity occur at higher processing temperatures within the above ranges.

[0274] In certain embodiments, the PAB, PEB, and / or PDB treatments can be performed at a gas atmosphere flow in the range of 100-10,000 sccm, with a water content in the amount of a few percent up to 100% (e.g., 20-50%), at a pressure between atmospheric pressure and vacuum, for a period of about 1-15 minutes, e.g., about 2 minutes.

[0275] These findings can be used to adjust process conditions to tailor or optimize processes for specific materials and circumstances. For example, the selectivity achieved for a given EUV dose with a PEB thermal treatment of 220-250°C in air at about 20% humidity for about 2 minutes can be similar to that achieved for about 30% higher EUV doses without such thermal treatment. Thus, depending on the selectivity requirements / constraints of the semiconductor processing operation, thermal treatments as described herein can be used to lower the required EUV dose. Alternatively, if higher selectivity is required and a higher dose can be tolerated, it is possible to obtain much higher selectivity (up to 100x exposed vs. unexposed) than is possible in wet development scenarios.

[0276] Yet other steps may include in situ metrology capable of assessing physical and structural properties (e.g., critical dimensions, film thickness, etc.) during the photolithography process. Modules for performing in situ metrology may include, for example, a scatterometry module, an ellipsometry module, a downstream mass spectrometry module, and / or a plasma-enhanced downstream optical emission spectroscopy module.

[0277] 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 metal-containing precursor in the presence of an optional ligand-containing precursor, a patterning module comprising an EUV photolithography tool having a radiation source with a wavelength of less than 30 nm, and a developing module comprising a chamber for developing the film.

[0278] The apparatus may further include a controller having instructions for such modules. In one embodiment, the controller includes one or more memory devices, one or more processors, and system control software coded with instructions for performing deposition of the film or capping layer. Such instructions may include depositing a resist film on top of the substrate or photoresist layer in a deposition module, patterning the film with a resolution of less than 30 nm directly by EUV exposure in a patterning module, thereby forming a pattern in the film, and developing the film in a development module. In a particular embodiment, the development module provides removal of EUV exposed or non-EUV exposed areas, thereby providing a pattern in the film.

[0279] 4 illustrates a schematic diagram of one embodiment of a process station 400 having a process chamber body 402 for maintaining a low pressure environment suitable for carrying out the described dry strip and development embodiments. Multiple process stations 400 may be included in a common low pressure process tool environment. For example, FIG. 5 illustrates one embodiment of a multi-station processing tool 500, such as a VECTOR® processing tool available from Lam Research, Inc. of Fremont, Calif. In some embodiments, one or more hardware parameters of the process station 400 (including those described in detail below) may be programmatically adjusted by one or more computer controllers 450.

[0280] The process stations can be configured as modules within a cluster tool. Figure 7 illustrates a semiconductor process cluster tool architecture having a vacuum integrated deposition and patterning module suitable for implementing the embodiments described herein. Such a cluster process tool architecture can include resist deposition, resist exposure (EUV scanner), resist dry development, and etching modules as described herein with reference to Figures 6 and 7.

[0281] In some embodiments, certain processing functions, such as dry developing and etching, can be performed sequentially in the same module. Also, embodiments of the present disclosure are directed to methods and apparatus for receiving a wafer including a photo-patterned EUV resist thin film layer disposed on a layer or layer stack to be etched, following photo-patterning in an EUV scanner, into a dry developing / etching chamber, dry developing the photo-patterned EUV resist thin film layer, and then etching the underlying layer using the patterned EUV resist as a mask, as described herein.

[0282] Returning to FIG. 4, the process station 400 is in fluid communication with a reactant delivery system 401a for delivering process gases to a distribution showerhead 406 via connection 405. The reactant delivery system 401a includes a mixing vessel 404 for blending and / or adjusting the process gases delivered to the showerhead 406. One or more mixing vessel inlet valves 420 can control the introduction of process gases to the mixing vessel 404. If plasma exposure is used, the plasma can also be delivered to the showerhead 406 or can be generated at the process station 400. The process gases can include any of those described herein, such as, for example, a metal-containing precursor, a ligand-containing precursor, or a back reactant.

[0283] 4 includes an optional vaporization point 403 for vaporizing a liquid reactant provided to the mixing vessel 404. The liquid reactant may include a metal-containing precursor, a ligand-containing precursor, or a reverse 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 that is vaporized and delivered to the process 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.

[0284] The showerhead 406 distributes process gases towards the substrate 412. In the embodiment depicted in Figure 4, the substrate 412 is shown positioned below the showerhead 406 and resting on a pedestal 408. The showerhead 406 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to the substrate 412.

[0285] In some embodiments, the pedestal 408 can 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 can be programmatically adjusted by a suitable computer controller 450.

[0286] In some embodiments, the pedestal 408 may be temperature controlled via heater 410. In some embodiments, the pedestal 408 may be heated to a temperature of greater than 0° C. to 300° C. or greater, such as 50-120° C., e.g., about 65-80° C., during non-plasma thermal exposure of the photopatterned resist to dry developing chemistries such as HBr, HCl, or BCl3 as described in disclosed embodiments.

[0287] Additionally, in some embodiments, pressure control for the process 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 for the process station 400 may also be adjusted by varying the flow rate of one or more gases introduced to the process station 400.

[0288] In some embodiments, the position of the showerhead 406 can be adjusted relative to the pedestal 408 to vary the volume between the substrate 412 and the showerhead 406. Further, 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 rotational axis for rotating the orientation of the substrate 412. It will be appreciated that in some embodiments, one or more of these exemplary adjustments can be implemented programmatically by one or more suitable computer controllers 450.

[0289] Where plasma may be used, for example in gentle plasma-based dry development embodiments 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 to power the plasma 407. In some embodiments, the plasma energy can 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 can 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.

[0290] In some embodiments, instructions for the controller 450 may be provided via 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, a process recipe step may be arranged in sequence such that all instructions for a process step are executed simultaneously with that process phase. 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 features described below with respect to the system controller 550 of FIG. 5.

[0291] As mentioned above, one or more process stations can be included in a multi-station processing tool. FIG. 5 shows a schematic diagram of an embodiment of a multi-station processing tool 500 with an inbound load lock 502 and an outbound load lock 504, either or both of which may include a remote plasma source. A robot 506 is configured to move a wafer from a cassette loaded via a pod 508 at atmospheric pressure to the inbound load lock 502 via an atmospheric pressure port 510. The wafer is placed by the robot 506 on a pedestal 512 of the inbound load lock 502, the atmospheric pressure port 510 is closed, and the load lock is pumped down. If the inbound load lock 502 includes a remote plasma source, the wafer may be subjected to a remote plasma treatment to treat the silicon nitride surface within the load lock before being introduced into the processing chamber 514. Additionally, the wafer may also be heated in the inbound load lock 502 to remove, for example, moisture and absorbed gases. A chamber transfer port 516 to the processing chamber 514 is then opened and another robot (not shown) places the wafer into the reactor on the pedestal of the first station shown in the reactor for processing. Although the embodiment illustrated in Figure 5 includes a load lock, it will be understood that in some embodiments the wafer may enter the process station directly.

[0292] The illustrated processing chamber 514 includes four process stations, numbered 1 through 4 in the embodiment shown in FIG. 5. Each station has a heated pedestal (shown at 518 for station 1) and a gas line inlet. It will be appreciated that in some embodiments, each process station may have a different purpose or multiple purposes. For example, in some embodiments, a process station may be switchable between a dry development mode and an etch process mode. Additionally or alternatively, in some embodiments, the processing chamber 514 may include one or more corresponding pairs of dry development and etch process stations. While the illustrated processing chamber 514 includes four stations, it will be appreciated that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments, a processing chamber may have three or fewer stations.

[0293] FIG. 5 illustrates one embodiment of a wafer handling system 590 for transferring wafers within the processing chamber 514. In some embodiments, the wafer handling system 590 can transfer wafers between various process stations and / or between process 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 one embodiment of a system controller 550 used to control the process conditions and hardware states of the process tool 500. The system controller 550 can include one or more memory devices 556, one or more mass storage devices 554, and one or more processors 552. The processor 552 can include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0294] In some embodiments, the system controller 550 controls all of the activity of the process tool 500. The system controller 550 executes system control software 558 that is stored in the mass storage device 554, loaded into the memory device 556, and executed on 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), and the like may be used for these purposes. In the following description, wherever "software" or "code" is used, functionally equivalent hard-coded logic may be used instead. The system control software 558 may include instructions for controlling the timing, mixture of gases, gas flow rates, chamber and / or station pressures, chamber and / or station temperatures, wafer temperatures, target power levels, RF power levels, substrate pedestal, chuck and / or susceptor positions, and other parameters of a particular process performed by the process tool 500. The system control software 558 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 the process tool components used to perform the various process tool processes. The system control software 558 may be coded in any suitable computer readable programming language.

[0295] In some embodiments, the system control software 558 may include input / output control (IOC) sequence instructions for controlling the various parameters mentioned above. In some embodiments, other computer software and / or programs stored on the mass storage device 554 and / or memory device 556 associated with the system controller 550 may be used. 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.

[0296] The substrate positioning program may include program code for process tool components used to load the substrate onto the pedestal 518 and control the spacing between the substrate and other parts of the process tool 500.

[0297] 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 to stabilize the pressure of the process station, and optionally, code for flowing gases to one or more process stations prior to deposition. The pressure control program may include code for controlling the pressure of the process station, for example, by adjusting a throttle valve in the exhaust system of the process station, gas flow to the process station, etc.

[0298] The heater control program may include code for controlling the current to a heating unit used to heat the substrate, or the heater control program may control the delivery of a heat transfer gas (such as helium) to the substrate.

[0299] The plasma control program can include code for setting RF power levels applied to process electrodes in one or more process stations in accordance with embodiments herein.

[0300] The pressure control program can include code for maintaining pressure in the reaction chamber according to embodiments herein.

[0301] 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 and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0302] 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. These parameters may be provided to a user in the form of a recipe and may be entered using a user interface.

[0303] 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 can be output at analog and digital output connections of the process tool 500. Non-limiting examples of process tool sensors that can be monitored include mass flow controllers, pressure sensors (such as pressure gauges), thermocouples, etc. Appropriately programmed feedback and control algorithms can be used with data from these sensors to maintain process conditions.

[0304] The system controller 550 can provide program instructions for carrying out the deposition process described above. The program instructions can control various process parameters such as DC power levels, RF bias power levels, pressure, temperature, etc. The instructions can control parameters for operating the dry development and / or etching processes according to various embodiments described herein.

[0305] The system controller 550 typically includes one or more memory devices and one or more processors configured to execute instructions such that the apparatus performs methods according to the disclosed embodiments. Machine-readable media containing instructions for controlling process operations according to the disclosed embodiments may be coupled to the system controller 550.

[0306] In some implementations, the system controller 550 is part of a system, such as may be part of the examples described above. Such systems may include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more processing platforms, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling system operations before, during, and after processing of a semiconductor wafer or substrate. Such electronics may be referred to as a "controller" and may control various components or subparts of one or more systems. The system controller 550 may be programmed to control any of the processes disclosed herein depending on the processing conditions and / or type of system. Such processes may include 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 motion settings, wafer loading and unloading from tools and other transfer tools connected or interlocked with the particular system, and / or wafer loading and unloading from load locks.

[0307] Broadly, the system controller 550 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, etc. 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, i.e., microcontrollers that execute program instructions (e.g., software). The program instructions may be instructions communicated to the system controller 550 in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for a system. The operational parameters may, in some embodiments, be part of a recipe defined by a process engineer to accomplish one or more processing steps in the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0308] The system controller 550 may, in some embodiments, be part of, or coupled to, a computer that is integrated or coupled with the system or otherwise networked to the system, or a combination thereof. For example, the system controller 550 may be in the "cloud" or all or part of a fab host computer system. This allows for remote access of wafer processing. The computer may allow remote access to the system to monitor the current progress of a fabrication operation, review the history of past fabrication operations, review trends or performance criteria from multiple fabrication operations, modify parameters of a current process, set processing steps following a current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide a process recipe to the system over a network. Such a network 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, which are then communicated from the remote computer to the system. In some examples, the system controller 550 receives instructions in the form of data. Such data identifies parameters for each processing step 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 that the system controller 550 is configured to interface with or control. Thus, as described above, the system controller 550 may be distributed, for example, by including one or more individual controllers that are networked together and cooperate toward a common purpose (such as the processes and controls described herein).An example of a distributed controller for such purposes would include one or more integrated circuits on the chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) and coupled to control the process in the chamber.

[0309] Exemplary systems may include, but are not limited to, 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 tracking 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.

[0310] As described above, depending on the process step or steps being performed by the tool, the system controller 550 may communicate with one or more 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 transport to and from tool locations and / or load ports within a semiconductor manufacturing factory.

[0311] In a particular embodiment, an inductively coupled plasma (ICP) reactor is described herein that may be suitable for etching operations suitable for practicing 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.

[0312] 6 illustrates generally a cross-sectional view of an inductively coupled plasma apparatus 600 suitable for performing certain embodiments or aspects of embodiments, such as dry development and / or etching, an example of which is the Kiyo® Reactor manufactured by Lam Research, Inc. 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.

[0313] The inductively coupled plasma apparatus 600 includes an overall etch chamber structurally defined by a chamber wall 601 and a window 611. The chamber wall 601 can be fabricated from stainless steel or aluminum. The window 611 can be fabricated from quartz or other dielectric materials. An optional internal plasma grid 650 divides the overall etch chamber into an upper sub-chamber 602 and a lower sub-chamber 603. In many embodiments, the plasma grid 650 can be removed, thereby utilizing the chamber space consisting of the sub-chambers 602 and 603. A chuck 617 is positioned within the lower sub-chamber 603 near the bottom inner surface. The chuck 617 is configured to receive and hold a semiconductor wafer 619 on which an etching process is performed. The chuck 617, if present, can be an electrostatic chuck for supporting the wafer 619. In some embodiments, an edge ring (not shown) surrounds the chuck 617 and, if present on the chuck 617, has an upper surface that is approximately planar with an upper surface of the wafer 619. The chuck 617 also includes an electrostatic electrode for chucking and dechucking the wafer 619. For this purpose, a filter and DC clamp power supply (not shown) may be provided.

[0314] Other control systems for lifting the wafer 619 from the chuck 617 may also be provided. The chuck 617 may be charged using an RF power supply 623. The RF power supply 623 is connected to a matching circuit 621 through a connection 627. The matching circuit 621 is connected to the chuck 617 through a connection 625. In this manner, the RF power supply 623 is connected to the chuck 617. In various embodiments, the bias power of the electrostatic chuck may be set to about 50V or may be set to a different bias power depending on the process being performed according to the disclosed embodiments. For example, the bias power may be about 20V to about 100V, or about 30V to about 150V.

[0315] The elements for plasma generation include a coil 633 positioned over the window 611. In some embodiments, a coil is not used in the disclosed embodiments. The coil 633 is fabricated from a conductive material and includes at least one complete turn. The exemplary coil 633 shown in FIG. 6 includes three turns. A cross section of the coil 633 is symbolically shown with the coil having an "X" rotating into the page while the coil having a "●" rotating out of the page. The elements for plasma generation also include an RF power source 641 configured to provide RF power to the coil 633. Generally, the RF power source 641 is connected to a matching circuit 639 through connection 645. The matching circuit 639 is connected to the coil 633 through connection 643. In this manner, the RF power source 641 is 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 spaced apart relationship relative to the coil 633. In some embodiments, the Faraday shield 649 is disposed directly above the window 611. In some embodiments, the Faraday shield is between the window 611 and the chuck 617. In some embodiments, the Faraday shield is not maintained in a spaced apart relationship to the coil 633. 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 can prevent metals or other species from depositing on the window 611 of the process chamber.

[0316] Process gases can flow into the process chamber via one or more main gas inlets 660 and / or one or more side gas inlets 670 positioned in the upper subchamber 602. Similarly, similar gas inlets, not explicitly shown, can 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, can be used to draw process gases from the process chamber and maintain pressure within the process chamber. For example, the vacuum pump can be used to evacuate the lower subchamber 603 during an ALD purge operation. A valve controlled conduit can 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 can be done 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 can also be used.

[0317] During operation of the apparatus 600, one or more reactant gases may be supplied through the injection ports 660 and / or 670. In certain embodiments, process gases may be supplied only through the main gas inlet 660 or only through the side gas inlet 670. In some cases, the gas inlets shown in the figure may be replaced with more complex gas inlets, such as one or more showerheads. The Faraday shield 649 and / or optional grid 650 may include internal channels and holes that allow delivery of process gases to the process chamber. Either or both of the Faraday shield 649 and 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 process chamber, whereby once the liquid reactant or precursor is vaporized, the vaporized reactant or precursor is introduced into the process chamber via the gas inlets 660 and / or 670.

[0318] Radio frequency power is supplied from an RF power source 641 to the coil 633, causing an RF current to flow through the coil 633. The RF current flowing through the coil 633 generates an electromagnetic field around the coil 633. The electromagnetic field generates an induced current in the upper subchamber 602. Physical and chemical interactions of the various generated ions and radicals with the wafer 619 etch features in the wafer 619 and selectively deposit layers on the wafer 619.

[0319] When a plasma grid 650 is used such that both an upper subchamber 602 and a lower subchamber 603 are present, induced currents act 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 limits the number of thermal electrons in the lower subchamber 603. In some embodiments, the apparatus 600 is designed and operated such that the plasma present in the lower subchamber 603 is an ion-ion plasma.

[0320] Both the upper electron-ion plasma and the lower ion-ion plasma can contain positive and negative ions, but the ion-ion plasma has a greater ratio of negative ions to positive ions. Volatile etch and / or deposition byproducts can be removed from the lower subchamber 603 through port 622. The chuck 617 disclosed herein can operate at elevated temperatures ranging from about 10 to 250° C. The temperature depends on the process operation and the particular recipe.

[0321] The apparatus 600 may be coupled to equipment (not shown) when installed in a clean room or fabrication facility. The equipment includes plumbing to provide process gases, vacuum, temperature control, and environmental particle control. These equipment will be coupled to the apparatus 600 when installed in the intended fabrication facility. Additionally, the apparatus 600 may be coupled to a transfer chamber that allows a robot to move semiconductor wafers in and out of the apparatus 600 using typical automated operations.

[0322] In some embodiments, a system controller 630 (which may include one or more physical or logical controllers) controls some or all of the operation of the process 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 the flow rates and duration when the disclosed embodiments are performed. 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 flowing chemistry, the selected recipe, the reactor architecture, and other factors.

[0323] In some implementations, the system controller 630 is part of a system, such a system 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 processing platforms, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling system operations before, during, and after processing of a semiconductor wafer or substrate. Such electronics may be integrated into the system controller 630 and control various components or subparts of the system or systems. The system controller may be programmed to control any of the processes disclosed herein depending on the processing parameters and / or type of system. Such processes may include 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 motion settings, wafer loading and unloading from tools and other transfer tools connected or interlocked with the particular system, and / or wafer loading and unloading from load locks.

[0324] Broadly, 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, etc. 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, i.e., microcontrollers that execute program instructions (e.g., software). The program instructions may be instructions communicated to the controller in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for a system. The operational parameters may, in some embodiments, be part of a recipe defined by a process engineer to accomplish one or more processing steps in the fabrication or removal of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0325] The system controller 630 may, in some embodiments, be part of, or coupled to, a computer that is integrated or coupled with the system or otherwise networked to the system, or a combination thereof. For example, the controller may be in the "cloud" or all or part of a fab host computer system. This allows for remote access of wafer processing. The computer may allow remote access to the system to monitor the current progress of a fabrication operation, review the history of past fabrication operations, review trends or performance criteria from multiple fabrication operations, modify parameters of a current process, set processing steps following a current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system over a network. Such a network 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, which are then communicated from the remote computer to the system. In some examples, the system controller 630 receives instructions in the form of data. Such data identifies parameters for each processing step 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 that the controller is configured to interface with or control. Thus, as described above, the system controller 630 may be distributed, for example, by including one or more individual controllers that are networked together and cooperate toward a common purpose (such as the processes and controls described herein).An example of a distributed controller for such purposes would include one or more integrated circuits on the chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) and coupled to control the process in the chamber.

[0326] Exemplary systems may include, but are not limited to, 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 tracking 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.

[0327] As described above, depending on the process step or steps being performed by the tool, the controller may communicate with one or more 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 transport to and from tool locations and / or load ports within a semiconductor manufacturing factory.

[0328] EUVL patterning can 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 standalone device from which substrates are loaded and unloaded for deposition and etching as described herein. Alternatively, as described below, the EUVL patterning tool may be a module on a larger multi-component tool. FIG. 7 illustrates a semiconductor process cluster tool architecture having a vacuum integrated deposition, EUV patterning, and dry develop / etch module interfaced with a vacuum transfer module suitable for carrying out the processes described herein. The processes can be performed without such vacuum integrated equipment, although such equipment may be advantageous in some embodiments.

[0329] FIG. 7 illustrates a semiconductor process cluster tool architecture having a vacuum integrated deposition and patterning module interfaced with a vacuum transfer module suitable for carrying out the processes described herein. The arrangement of transfer modules to "transfer" wafers between multiple storage facilities and processing modules is sometimes referred to as a "cluster tool architecture" system. The deposition and patterning modules are vacuum integrated according to the requirements of a particular process. Other modules, such as for etching, can also be included in the cluster.

[0330] A vacuum transport module (VTM) 738 interfaces with four processing modules 720a-720d, which can be individually optimized to perform various fabrication processes. By way of example, processing modules 720a-720d can be implemented to perform deposition, evaporation, ELD, dry develop, etch, strip, and / or other semiconductor processes. For example, module 720a can be an ALD reactor that can be operated to perform non-plasma thermal atomic layer deposition as described herein, such as a Vector tool available from Lam Research, Inc., Fremont, Calif., and module 720b can be a PECVD tool, such as a Lam Vector®. It should be understood that the figures are not necessarily drawn to scale.

[0331] Airlocks 742 and 746, also known as loadlocks or transfer modules, interface with the VTM 738 and the patterning module 740. For example, as mentioned above, a suitable patterning module can be a TWINSCAN NXE:3300B® platform supplied by ASML, Veldhoven, The Netherlands. This tool architecture allows workpieces, such as semiconductor substrates or wafers, to be transferred under vacuum so that they do not react before exposure. The integration of the deposition module with the lithography tool is facilitated by the fact that EUVL also requires a significantly reduced pressure, given the strong optical absorption of incident photons by ambient gases such as H2O, O2, etc.

[0332] As mentioned above, this integrated architecture is only one possible embodiment of a tool for carrying out the described process. The process can also be carried out with more conventional standalone EUVL scanners and as a module, a deposition reactor such as a Lam Vector tool, e.g., as described with reference to FIG. 7 but without an integrated patterning module, either standalone or integrated in a cluster architecture with other tools such as etch, strip, etc. (e.g., Lam Kiyo or Gamma tools).

[0333] Airlock 742 may be an "out" load lock, referring to the transfer of substrates from the VTM 738 servicing deposition module 720a to the patterning module 740, and airlock 746 may be an "in" load lock, referring to the transfer of substrates from the patterning module 740 back to the VTM 738. The in load lock 746 may also provide an interface to the outside of the tool for access and egress of substrates. Each process module has a facet that interfaces the module to the VTM 738. For example, deposition process module 720a has facet 736. Within each facet, sensors, such as sensors 1-18 shown, are used to detect the passage of wafer 726 as it moves between the respective stations. Patterning module 740 and airlocks 742 and 746 may similarly include additional facets and sensors not shown.

[0334] 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 that lifts a wafer such as wafer 726 for transfer. A front-end robot 744 is used therein to transfer wafers 726 from the exit airlock 742 to the patterning module 740 and from the patterning module 740 to the entry airlock 746. The front-end robot 744 can also transfer wafers 726 between the entry loadlock and the exterior of the tool for substrate access and egress. Because the entry airlock module 746 has the ability to adapt the environment between atmospheric pressure and vacuum, the wafers 726 can move between the two pressure environments without being damaged.

[0335] It should be noted that EUVL tools typically operate at a higher vacuum than deposition tools. In this case, it is desirable to increase the vacuum environment of the substrate during transfer between the deposition and EUVL tools to allow for outgassing of the substrate before entering the patterning tool. The unloading airlock 742 can provide this function by holding the transferred wafer at a low pressure, no higher than the pressure in the patterning module 740 for a period of time, and venting the off-gassing, so that the optics of the patterning tool 740 are not contaminated by off-gassing from the substrate. A suitable pressure for the venting off-gas airlock is 1E-8 Torr or less.

[0336] In some embodiments, a system controller 750 (which may include one or more physical or logical controllers) controls some or all of the operations of the cluster tool and / or its separate modules. Note that the controller may be local to the cluster architecture, or may be located outside the cluster architecture on the manufacturing floor, or may be located at a remote location and connected to the cluster architecture via a network. The system controller 750 may include one or more memory devices 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 are executed on the processor to perform appropriate control operations. These instructions may be stored in a memory device associated with the controller or provided over a network. In certain embodiments, the system controller executes system control software.

[0337] The system control software may include instructions for controlling the timing of application 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 process tool processes. 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) sequence instructions for controlling the various parameters described above. For example, each stage of a semiconductor fabrication process may include one or more instructions executed by the system controller. For example, instructions for setting process conditions for condensation, deposition, evaporation, patterning, and / or etching stages may be included in the corresponding recipe stages.

[0338] In various embodiments, an apparatus for forming a negative pattern mask is provided. The apparatus can include a process chamber for patterning, deposition, and etching, and a controller including instructions for forming the negative pattern mask. The instructions can include code for patterning features in a chemically amplified (CAR) resist on a semiconductor substrate by EUV exposure in the process chamber to expose a surface of the substrate, dry developing the photopatterned resist, and etching an underlying layer or layer stack using the patterned resist as a mask.

[0339] It should be noted that the computer controlling the movement of the wafers may be local to the cluster architecture, or may be located outside the cluster architecture on the manufacturing floor, or may be located at a remote location and connected to the cluster architecture via a network.

[0340] conclusion Although the foregoing embodiments have been described in some detail for clarity of understanding, it will be apparent that certain changes and modifications may be practiced 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 disclosed embodiments. Furthermore, while the disclosed embodiments are described in conjunction with specific embodiments, it will be understood that the specific embodiments are not intended to limit the disclosed embodiments. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatus of the present embodiments. Thus, the present embodiments should be considered as illustrative rather than limiting, and the embodiments should not be limited to the details set forth herein.

Claims

1. A patterning radiation sensitive film comprising an organometallic-oxo material, the material comprising a metal, oxygen, and C. 1-4 Haloaliphatic or C 1-4 The C 1-4 The aliphatic group is C 1-2 Alkyl, C 2-4 Alkenyl, and C 2-4 alkynyl.

2. 2. The membrane of claim 1 , The metal is tin (Sn).

3. 2. The membrane of claim 1 , Said C 1-4 Haloaliphatic is C 1-4 Haloalkyl, C 2-4 Haloalkenyl, and C 2-4 haloalkynyl.

4. 2. The membrane of claim 1 , Said C 1-4 Haloalkyl includes halo-substituted methyl containing 1, 2, or 3 halo substituents, or β-halo-substituted ethyl containing 1, 2, or 3 halo substituents.

5. 2. The membrane of claim 1 , Said C 1-4 The haloaliphatic includes one or more fluoro or iodo substituents.

6. 2. The membrane of claim 1 , Said C 1-4 The aliphatic is selected from the group consisting of methyl, ethyl, vinyl, ethynyl, propenyl, and propargyl.

7. 2. The membrane of claim 1 , The dose of the film versus gel is 3-4 The dose of non-halogenated membranes containing alkyl is lower than that of gels.

8. 2. The membrane of claim 1 , a vertical gradient extending from the upper surface of the membrane to a lower portion of the membrane, the upper portion being 3-4 alkyl group, and the lower portion is 1-4 Haloaliphatic Groups, C 1-2 Alkyl group, C 2-4 Alkenyl group, or C 2-4 A membrane comprising an alkynyl group.

9. 2. The membrane of claim 1 , The material is a metal-oxygen bond and a metal-C 1-4 Haloaliphatic bond or metal-C 1-4 A membrane comprising a network of aliphatic bonds.

10. A membrane according to any one of claims 1 to 9, The patterning radiation sensitive film comprises an extreme ultraviolet (EUV) sensitive film.

11. A method using a resist, comprising the steps of: depositing a metal-containing precursor on a surface of a substrate to provide a resist film, the resist film comprising a metal, oxygen, and C. 1-4 Haloaliphatic or C 1-4 Contains aliphatic Said C 1-4 Haloaliphatic is C 1-4 Haloalkyl, C 2-4 Haloalkenyl, and C 2-4 haloalkynyl; Said C 1-4 The aliphatic group is C 1-2 Alkyl, C 2-4 Alkenyl, and C 2-4 alkynyl, method.

12. 12. The method of claim 11, The metal-containing precursor has formula (I): M a R b L c (I) The structure has a Each M is independently a metal (e.g., tin (Sn)); Each R is independently an optionally substituted C 1-4 Haloalkyl, optionally substituted C 2-4 Haloalkenyl, optionally substituted C 2-4 Haloalkynyl, optionally substituted C 1-2 Alkyl, optionally substituted C 2-4 alkenyl, or optionally substituted C 2-4 Alkynyl each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety reactive with a reverse reactant and / or a ligand-containing precursor; a ≧ 1, b ≧ 1, and c ≧ 1; method.

13. 13. The method of claim 12, The metal-containing precursor has the formula (Ia): SnR b L 3-b (Yes) The structure has a Each R is independently an optionally substituted C 1-4 Haloalkyl, optionally substituted C 2-4 Haloalkenyl, optionally substituted C 2-4 Haloalkynyl, optionally substituted C 1-2 Alkyl, optionally substituted C 2-4 alkenyl, or optionally substituted C 2-4 is alkynyl, each L is independently halo, optionally substituted amino, optionally substituted alkoxy, or a ligand that reacts with a reverse reactant and / or a ligand-containing precursor; b is 1 or 2; method.

14. 12. The method of claim 11, The method, wherein said depositing comprises simultaneously or sequentially providing said metal-containing precursor with a ligand-containing precursor.

15. 15. The method of claim 14, The metal-containing precursor has formula (III): M a L c (III) The structure has a each M is independently a metal (e.g., Sn(II)); each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety reactive with a reverse reactant and / or a ligand-containing precursor; a ≧ 1, and c ≧ 1; method.

16. 16. The method of claim 15, The ligand-containing precursor has the formula (IV): R f L g (IV) The structure has a Each R is independently an optionally substituted C 1-4 Haloalkyl, optionally substituted C 2-4 Haloalkenyl, optionally substituted C 2-4 Haloalkynyl, optionally substituted C 1-2 Alkyl, optionally substituted C 2-4 alkenyl, or optionally substituted C 2-4 is alkynyl, each L is independently halo, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, a ligand, an ion, or a moiety reactive with a reverse reactant; f≧1, and g≧1; method.

17. 17. The method of claim 16, The method of claim 1, wherein the metal-containing precursor having formula (III) is reacted with the ligand-containing precursor having formula (IV) to provide a precursor having a structure having formula (I).

18. 12. The method of claim 11, The method, wherein said depositing comprises providing said metal-containing precursor and optional ligand-containing precursor in vapor form.

19. 12. The method of claim 11, The method, wherein the depositing further comprises a second metal-containing precursor to form an upper portion of the film, thereby providing a gradient film.

20. 12. The method of claim 11, The method, wherein said depositing further comprises providing a reverse reactant.

21. 21. The method of claim 20, The method, wherein the reverse reactant comprises water vapor.

22. 12. The method of claim 11, The method, wherein the resist film comprises an extreme ultraviolet (EUV) sensitive film.

23. 12. The method of claim 11, The method, wherein the resist film comprises an organotinoxy, an organotin oxide, an organotin oxide hydroxide, a haloorganotinoxy, a haloorganotin oxide, or a haloorganotin oxide hydroxide.

24. 2. The method of claim 1 , The metal of the resist film comprises tin (Sn), and the C of the resist film 1-4 The method wherein the haloaliphatic comprises a halo-substituted methyl containing 1, 2, or 3 halo substituents, or a β-halo-substituted ethyl containing 1, 2, or 3 halo substituents.

25. 2. The method of claim 1 , The resist film has a metal-oxygen bond and a metal-C bond. 1-4 Haloalkyl bond or Metal-C 1-2 A method comprising providing an organometallic-oxo material comprising a network of alkyl bonds.

26. 2. The method of claim 1 , The dose vs. gel of the resist film is affected by metal, oxygen, and C. 3-4 The method provides a lower dose to gel for non-halogenated films with alkyl groups.

27. 12. The method of claim 11, patterning the resist film by exposing it to patterned radiation, thereby providing an exposed film having radiation-exposed and non-radiation-exposed areas; developing the exposed film, thereby removing the radiation-exposed areas to provide a pattern in a positive resist film, or removing the radiation-unexposed areas to provide a pattern in a negative resist. The method further comprises:

28. 28. The method of claim 27, The method, wherein said patterning comprises EUV exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum atmosphere.

29. 28. The method of claim 27, The method, wherein said developing comprises dry developing or wet developing.

30. 30. The method of claim 29, A method wherein said dry development is used with an exposed film containing tin bonded to fluorine or iodine atoms.

31. An apparatus for forming a resist film, comprising: a deposition module including a chamber for depositing a resist film; a controller including one or more memory devices, one or more processors, and system control software, the system control software comprising: The deposition module is encoded with instructions including machine-readable instructions for depositing a metal-containing precursor and an optional ligand-containing precursor on an upper surface of a semiconductor substrate to form the resist film, the resist film comprising a metal, oxygen, and C. 1-4 Haloaliphatic or C 1-4 The C 1-4 The aliphatic group is C 1-2 Alkyl, C 2-4 Alkenyl, and C 2-4 alkynyl, Device.

32. 32. The apparatus of claim 31 , The apparatus, wherein the resist film comprises an extreme ultraviolet (EUV) sensitive film.

33. 32. The apparatus of claim 31 , 1. A patterning module comprising a photolithography tool having a radiation source at a wavelength less than 300 nm, the instructions including machine readable instructions for: In the patterning module, the resist film is directly patterned with a resolution of less than 300 nm by patterning radiation exposure, thereby forming an exposed film having radiation-exposed and radiation-unexposed regions. A patterning module further comprising instructions for: The apparatus further comprises:

34. 34. The apparatus of claim 33, The apparatus, wherein the source for the photolithography tool is a radiation source with a wavelength of less than 30 nm.

35. 35. The apparatus of claim 34, The instructions including machine readable instructions: In the patterning module, the resist film is directly patterned with EUV exposure at a resolution of less than 30 nm, thereby forming the exposed film having EUV exposed areas and EUV non-exposed areas. The apparatus further comprises instructions for:

36. 34. The apparatus of claim 33, a developing module comprising a chamber for developing the resist film, the instructions including machine readable instructions for: In the developing module, developing the exposed film removes either the radiation exposed areas or the radiation unexposed areas to provide a pattern in the resist film. a development module further comprising instructions for The apparatus further comprises:

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