Development of hybrid organotin oxide photoresists

Abstract

The present disclosure relates to films formed using organometallic precursors and organic co-reactants, and methods of forming and using such films. In certain embodiments, the films can be incubated after exposure to radiation, which can enhance the material difference between exposed and unexposed regions. In non-limiting embodiments, the radiation can include extreme ultraviolet (EUV) radiation or deep ultraviolet (DUV) radiation.

Description

[Technical field]

[0001] Incorporation by Reference A PCT application is being filed contemporaneously herewith as a part of this application. Each application to which this application claims benefit or priority, as identified in the contemporaneously filed PCT application, is hereby incorporated by reference in its entirety for all purposes.

[0002] The present disclosure relates to films formed using organometallic precursors and organic co-reactants, and methods of forming and using such films. In certain embodiments, the films can be incubated after exposure to radiation, which can further enhance the material differentiation between exposed and unexposed regions. In non-limiting embodiments, the radiation can include extreme ultraviolet (EUV) radiation or deep ultraviolet (DUV) radiation. [Background technology]

[0003] The background art description provided herein is intended to provide a general overview of the present technology. Work by the currently named inventors within the scope of this background art 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 to 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 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 induces 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 22 nm, 16 nm, and beyond. For example, at the 16 nm node, the width of a via or line in a damascene structure may be 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 allows for the extension of lithography techniques by moving to shorter imaging source wavelengths than can be achieved with photolithography methods. EUV sources with wavelengths of approximately 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 and water vapor, and therefore operates in a vacuum. Summary of the Invention

[0007] The present disclosure relates to the use of organometallic precursors and organic co-reactants to prepare patterned radiation sensitive films. In one example, the precursor may be an organometallic compound that may be deposited to provide a metal-containing photoresist, and the organic co-reactant may be used to interact with the precursor during deposition. Such interaction may not result in deposition of the organic co-reactant within the film, but may nevertheless affect the composition or properties of the film.

[0008] In another example, the precursor can be an organometallic compound that can be deposited to prepare a metal-containing photoresist, and an organic co-reactant can be used to react with the precursor during deposition. Such a reaction can result in a modified precursor that can be deposited in the film. Furthermore, the modified precursor can have a radiation-responsive organic moiety provided by the organic co-reactant and a radiation-sensitive metal center provided by the precursor. In a non-limiting embodiment, the radiation can include extreme ultraviolet (EUV) or deep ultraviolet (DUV) radiation.

[0009] Films can be prepared by using such organometallic precursors with organic co-reactants, which can then be incubated under conditions that enhance the material difference between exposed and unexposed regions. Such post-exposure incubation can improve the sensitivity of the film to a particular radiation dose. For example, an incubated film can have a lower dose-to-clear (DtC), or dose-to-gel (DtG), or dose-to-size (DtS) compared to an exposed film (not incubated). In this way, the same underlying film can be optimized for high- or low-dose applications by adjusting the incubation conditions. Non-limiting incubation conditions include control of temperature, atmosphere, humidity, and / or time, as described herein.

[0010] Furthermore, by introducing this incubation step, various different developers can be selected to distinguish between lithographically exposed and unexposed regions. In one non-limiting example, by selecting specific incubation conditions, it was possible to develop using pH-neutral water with a lower DtG threshold. As described herein, other developers such as aqueous solutions, organic solutions, or gaseous acids may also be used.

[0011] In certain embodiments, the method includes selecting specific incubation conditions and specific types of developers to achieve the desired functionality of the film. In this way, the same film can be used for different applications by adjusting the incubation and developer conditions, which means great flexibility of the material for different lithography applications (e.g., high-dose, low-roughness applications and low-dose, high-throughput applications). Furthermore, different types and combinations of one or more organometallic precursors and one or more organic co-reactants can be used to adjust the composition of the deposited film.

[0012] Thus, in a first aspect, the disclosure encompasses a method of using a resist comprising delivering an organometallic precursor to a surface of a substrate in the presence of an organic co-reactant to prepare a resist film, patterning the resist film by exposure to patterned radiation to thereby provide an exposed film having radiation exposed and non-radiation exposed areas, incubating the exposed film at a temperature of about 20-300° C., thereby providing an incubated film, and developing the incubated 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.

[0013] In some embodiments, the resist film comprises an extreme ultraviolet (EUV) sensitive film. In other embodiments, the resist film comprises an organotin acetylide oxide, a tin acetylide oxide, a tin acetylide telluride, an organotin oxalate, a tin oxalate, an organotin formate, a tin formate, an organotin peroxide, or a tin peroxide.

[0014] In some embodiments, preparing the resist film may include depositing a modified precursor on the surface of the substrate to prepare the resist film. In certain embodiments, the modified precursor is formed by reacting an organometallic precursor (e.g., any described herein) with an organic co-reactant (e.g., any described herein). In other embodiments, the precursor includes an organometallic compound having one or more ligands, and the organic co-reactant replaces at least one of the ligands to provide the modified precursor. In some embodiments, the modified precursor is characterized by increased EUV absorption or increased EUV absorption cross-section compared to the organometallic precursor. In other embodiments, the modified precursor includes increased or decreased carbon content compared to the organometallic precursor.

[0015] In some embodiments, the dose to clear or dose to gel of the incubated membrane is lower than that of the exposed membrane. In other embodiments, the patterning is performed at about 1-50 mJ / cm 2 , 1~40mJ / cm 2 , 1~30mJ / cm 2 , 1~20mJ / cm 2 , or 1 to 10 mJ / cm 2 Includes radiation dose.

[0016] In some embodiments, the organometallic precursor comprises at least one ligand and the organic co-reactant replaces at least one ligand to provide the modified precursor, hi other embodiments, the modified precursor is deposited in vapor form.

[0017] In other embodiments, the method further comprises providing a molar ratio of the organometallic precursor to the organic co-reactant of from about 1000: 1 to about 1: 4. In certain embodiments, such providing can comprise delivering the organometallic precursor in vapor form and the organic co-reactant in vapor form to a chamber containing the semiconductor substrate.

[0018] 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.

[0019] In some embodiments, the patterning further comprises the release of carbon dioxide and / or carbon monoxide from the exposed film. In other embodiments, the patterning further comprises photopolymerization occurring within the exposed film. In certain embodiments, the organic co-reactant and / or film comprises a photopolymerizable moiety. In further embodiments, the photopolymerizable moiety comprises an optionally substituted alkenylene, an optionally substituted alkynylene, or an optionally substituted epoxy (e.g., an optionally substituted oxiranyl). In still other embodiments, the organic co-reactant and / or film comprises an alkynyl moiety, a carbonyl moiety, a dicarbonyl moiety, or a haloalkyl moiety.

[0020] In some embodiments, the incubation comprises an optional period of time of about 30-300 seconds, in an ambient atmosphere, at a temperature of about 100-200° C. In certain embodiments, the incubation comprises a temperature of about 100-180° C., 100-250° C., 120-200° C., 120-250° C., or 120-280° C.

[0021] In other embodiments, the incubation comprises a temperature of about 20-30° C. for a period of about 1-7 days. In certain embodiments, the incubation can comprise an inert atmosphere or an ambient atmosphere having optional humidity (e.g., room humidity (RH), 10% RH, 90 RH%, and ranges therein).

[0022] In still other embodiments, the incubation comprises a temperature of about 100-300° C. in an inert atmosphere having an optional humidity for an optional time of about 1-300 seconds. In some embodiments, the incubation comprises a temperature of about 150-300° C., 180-300° C., 100-250° C., or 150-250° C. In certain embodiments, the incubation may comprise an inert atmosphere or an ambient atmosphere having an optional degree of humidity (e.g., room humidity (RH), 10% RH, 90 RH%, and ranges therein).

[0023] In some embodiments, the developing step comprises removing radiation-exposed areas to provide a pattern in a positive resist film, while in other embodiments, the developing step comprises removing radiation-unexposed areas to provide a pattern in a negative resist film.

[0024] In some embodiments, the developing comprises wet developing or dry developing. Non-limiting wet developing can comprise water, an acid, a base, a ketone, an ester, an alcohol, an ether, or a combination thereof, for an optional time of about 15 to 60 seconds. In further embodiments, the wet developing further comprises one or more surfactants. In other embodiments, dry developing comprises gaseous water, oxygen (O), at an optional pressure of about 0.1 to 1 Torr, for an optional time of about 30 to 720 seconds. 2 ), gaseous acids, gaseous halides, or combinations thereof.

[0025] In other embodiments, the incubating comprises a temperature of about 100-250° C. in an ambient atmosphere, and the developing comprises water in liquid or vapor form.

[0026] In yet another embodiment, the incubating comprises a temperature of about 20-30° C. for a period of about 1-7 days, and the developing comprises the addition of water, oxygen (O 2 ), ketones or liquid water in conjunction with dry development processes that include gaseous acids, gaseous halides, or combinations thereof.

[0027] In a second aspect, the disclosure features an apparatus for forming a resist film, the apparatus including a deposition module, a patterning module, an incubating module, a developing 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.

[0028] In some 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), which may be configured to accommodate a semiconductor substrate. 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 radiation source may be a radiation source with a wavelength of less than 30 nm). In yet other embodiments, the incubate module includes a chamber for incubating the resist film, which may be configured to control one or more incubation conditions (e.g., any of the conditions herein, such as temperature, atmospheric content, humidity, and / or duration). In some embodiments, the develop module includes a chamber for developing the resist film.

[0029] In further embodiments, the instructions include machine-readable instructions for effecting deposition of an organometallic precursor on an upper surface of a semiconductor substrate in the presence of an organic co-reactant (e.g., in a deposition module) to form a resist film. In some embodiments, such deposition can form a resist film comprising an organotin acetylide oxide, tin acetylide oxide, tin acetylide telluride, organotin oxalate, tin oxalate, organotin formate, tin formate, organotin peroxide, or tin peroxide. In other embodiments, such deposition can form a patterned radiation-sensitive film as the resist film, wherein the organometallic precursor is provided in the presence of an organic co-reactant. In other embodiments, such deposition can include effecting a change in the molar ratio of the organometallic precursor to the organic co-reactant to form the patterned radiation-sensitive film.

[0030] In some embodiments, causing deposition may include depositing a modifying precursor on an upper surface of a semiconductor substrate to form a resist film, wherein the organometallic precursor is provided in the presence of an organic co-reactant to provide the modifying precursor.

[0031] In some embodiments, the instructions include machine-readable instructions for patterning (e.g., in a 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 at a resolution 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. In some embodiments, such patterning is performed at a radiation exposure of about 1-50 mJ / cm. 2 , 1~40mJ / cm 2 , 1~30mJ / cm 2 , 1~20mJ / cm 2 , or 1 to 10 mJ / cm 2 Includes radiation dose.

[0032] In some embodiments, the instructions include incubating the exposed membrane (e.g., in an incubating module) at a temperature of about 20-300° C., thereby resulting in an incubated membrane. In other embodiments, such incubation may include a temperature of about 100-250° C. in an ambient atmosphere for an optional time of about 30-300 seconds, a temperature of about 20-30° C. for a period of about 1-7 days, or a temperature of about 150-300° C. in an inert atmosphere with optional humidity for an optional time of about 1-300 seconds.

[0033] In still other embodiments, the instructions include machine-readable instructions for causing development of the incubated film (e.g., in a 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. In some embodiments, such developing may include delivering one or more of the following to the developing module: water, an acid, a base, a ketone, an ester, an alcohol, an ether, a surfactant, or combinations thereof. In other embodiments, such developing may include delivering one or more of the following: gaseous water, oxygen (O 2), a gaseous acid, a gaseous halide, or a combination thereof, to the development module.

[0034] In any embodiment herein, the patterning radiation sensitive film comprises an extreme ultraviolet (EUV) sensitive film, a deep ultraviolet (DUV) sensitive film, a photoresist film, or a photopatternable film.

[0035] In any of the embodiments herein, the patterned radiation-sensitive film comprises a plurality of polymerizable moieties (eg, photopolymerizable moieties), alkenylene moieties, alkynylene moieties, carbonyl moieties, or dicarbonyl moieties.

[0036] In any embodiment herein, the patterned radiation sensitive film comprises an organometallic or organometallic oxide material.

[0037] In any embodiment herein, the organometallic precursor comprises a structure having formula (I), (Ia), (III), (IV), (V), (VI), (VII), or (VIII) as described herein.

[0038] In any embodiment herein, the organometallic precursor has the formula (I): M a R b L c (I) where M is a metal or metalloid (e.g., any of those herein); 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 reactive with an organic co-reactant or counter-reactant, and R and L, together with M, can optionally form a heterocyclyl group, or R and L, together with M, can optionally form a heterocyclyl group, including structures with a > 1 (e.g., a is 1, 2, or 3), b > 1 (e.g., b is 1, 2, 3, 4, 5, or 6), and c > 1 (e.g., c is 1, 2, 3, 4, 5, 6).

[0039] In some embodiments, each R is L and / or M is tin (Sn), such as Sn(IV) or Sn(II). In other embodiments, each L is independently H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy (e.g., any L described herein).

[0040] In any of the embodiments herein, the organic co-reactant comprises a structure having formula (II), (IIa), (IIb), (IIc), (IId), or (IIe) described herein.

[0041] In any of the embodiments herein, the organic co-reactant comprises one or more polymerizable moieties, alkynyl moieties, carbonyl moieties, dicarbonyl moieties, or haloalkyl moieties. In some embodiments, the organic co-reactant has the formula (II): X 1 -ZX 2 (II) (In the formula, X 1 and X 2each is independently a leaving group (e.g., halo, H, hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, or optionally substituted aryl) and Z is carbonyl, dicarbonyl, optionally substituted alkylene, optionally substituted haloalkylene, optionally substituted alkenylene, or optionally substituted alkynylene).

[0042] In any embodiment herein, the organic co-reactant has a vapor pressure of about 0.1 mTorr to about 100 mTorr (eg, 0.1 mTorr to 50 mTorr or 0.5 mTorr to 100 mTorr).

[0043] In any of the embodiments herein, the organometallic precursor comprises an organometallic compound having one or more ligands (e.g., at least one ligand). In further embodiments, the organic co-reactant replaces at least some significant, detectable proportion of one ligand to provide a modified precursor. In other embodiments, the organic co-reactant replaces at least one of the ligands of the organometallic precursor to provide a modified precursor. In some embodiments, the detectable proportion is at least about 0.1%, 0.5%, 1%, or 3%, and between 0.1% and 5%.

[0044] In some embodiments herein, a single organometallic precursor is used with one or more organic co-reactants, while in other embodiments, two, three, four or more different organometallic precursors are used within one or more organic co-reactants.

[0045] In some embodiments herein, a single organometallic precursor is used with a single organic co-reactant. In other embodiments, a single organometallic precursor is used with two, three, four, or more different organic co-reactants. In yet other embodiments, two or more different organometallic precursors are used with a single organic co-reactant. In other embodiments, two or more different organometallic precursors are used with two or more different organic co-reactants.

[0046] In any embodiment herein, the molar ratio of the organometallic precursor to the organic co-reactant is from about 1000:1 to about 1:4 (eg, from about 1000:1 to 1:4, 100:1 to 10:1, 50:1 to 1:4, etc.).

[0047] In any embodiment herein, depositing comprises depositing a modified precursor in vapor form. In other embodiments, said depositing comprises providing an organometallic precursor, an organic co-reactant, and / or a counter 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.

[0048] In any of the embodiments herein, the modified precursor includes the use of a chalcogenide precursor or an oxygen-containing corresponding reactant.

[0049] In any embodiment herein, the providing or depositing further comprises providing a corresponding reactant. Non-limiting corresponding reactants include oxygen or a chalcogenide precursor, as well as any of those described herein (e.g., oxygen (O 2 ), ozone (O 3), oxygen-containing corresponding reactants including 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 provided below.

[0050] definition "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 Alkenyl groups can also be substituted or unsubstituted. For example, alkenyl groups can be substituted with one or more of the substituents described herein for alkyl.

[0051] "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 3-24 Alkenylene groups can be substituted or unsubstituted. For example, alkenylene groups can be substituted with one or more of the substituents described herein for alkyl. Exemplary, non-limiting alkenylene groups include -CH=CH- or -CH=CHCH 2 -- are some examples.

[0052] "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 , C1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 Examples of the alkyl group include alkoxy groups.

[0053] The terms "alkyl" and "alk" refer to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), cyclopropyl, n-butyl (n-Bu), isobutyl (i-Bu), s-butyl (s-Bu), t-butyl (t-Bu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. An alkyl group can be cyclic (e.g., C 3-24 The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may include a haloalkyl, in which the alkyl group is substituted with one or more halo groups as described herein. In another example, the alkyl group may be substituted with one, two, three, or, in the case of an alkyl group having two or more carbons, four, substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., -O-Ak, where Ak is an optionally substituted C 1-6 (2) amino (e.g., -NR N1 R N2 , R N1 and R N2 Each of is independently H or optionally substituted alkyl, or R N1 and R N2each 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., -CO 2 H), (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 2 ), (17) oxo (e.g., ═O), (18) —CO 2 R 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 1-6alkyl (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) (C 4-18 Aryl)C 1-6 alkyl (e.g., Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (h) C 3-8 cycloalkyl, and (i) (C 3-8 Cycloalkyl)C 1-6 In some embodiments, the unsubstituted alkyl group is selected from the group consisting of 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 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 It is an alkyl group.

[0054] "Alkylene" refers to the polyvalent (e.g., divalent) forms of the alkyl groups described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, an alkylene group is a C1-3 , 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 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.

[0055] "Alkynyl" refers to an optionally substituted C alkyl group having one or more triple bonds. 2-24 It means an alkyl group. An alkynyl group can be cyclic or acyclic, and is exemplified by ethynyl, 1-propynyl, and the like. An alkynyl group can also be substituted or unsubstituted. For example, an alkynyl group can be substituted with one or more of the substituents described herein for alkyl.

[0056] "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 Alkynylene groups are alkyl groups. Alkynylene groups can be cyclic or non-cyclic. Alkynylene groups can be substituted or unsubstituted. For example, alkynylene groups can be substituted with one or more substituents described herein for alkyl. Exemplary, non-limiting alkynylene groups include -C≡C- or -C≡CCH 2 -- are some examples.

[0057] "Amino" means -NR N1 R N2 means R N1 and R N2 is independently H, optionally substituted alkyl, or optionally substituted aryl, or RN1 and R N2 together with the nitrogen atom to which each is attached form a heterocyclyl group, as defined herein.

[0058] "Aminoalkyl" means an alkyl group, as defined herein, substituted by an amino group, as defined herein.

[0059] "Aminoaryl" means an aryl group, as defined herein, substituted by an amino group, as defined herein.

[0060] "Aryl" refers to fused benzo-C groups, such as, but not limited to, indanyl, tetrahydronaphthyl, and fluorenyl. 4-8 It refers to a group that includes 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 includes 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 includes 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 any of those described herein for alkyl.

[0061] "Carbonyl" refers to the group -C(O)-, which also can be represented as >C=O.

[0062] "Cycloalkyl," unless otherwise specified, means a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group having three to eight carbons, and is 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.

[0063] "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 independently is H or an optional substituent as set forth 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 R 4a each is independently H or an optional substituent as set forth for alkyl as defined herein. Non-limiting dicarbonyl moieties include, for example, -C(O)-C(O).

[0064] "Halo" means F, Cl, Br, or I.

[0065] "Haloalkyl" means an alkyl group, as defined herein, that is substituted with one or more halo.

[0066] "Haloalkylene" means an alkylene group, as defined herein, that is substituted with one or more halo.

[0067] "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 1, 2, or 3 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. Examples of the heterocycle 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, and benzodithi. inyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl,benzoxazepinyl, benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl, benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytosinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzoisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, Dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzooxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroipyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, 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, indolyl (e.g., 1H-indo aryl or 3H-indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazolyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidinyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthoindazolyl, naphthindolyl, naphthyridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl,naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanoyl, oxetanyl, oxetyl, oxtenyl, oxindolyl, oxiranyl, oxobenzisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, nothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyrronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolizidinyl aryl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenadinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydropyranyl, tetrahydropyryl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydropyryl, tetrahydropyryl, tetrahydropyryl, tetrahydropyryl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydropyryl, tetrahydropyryl, tetrahydropyryl, tetrahydropyryl, tetrahydroquinolyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydropyr ...pyryl, tetrahydroquinolyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydro 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,Examples of heterocyclyl groups include thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, urisyl, uridinyl, xanthenyl, xanthinyl, xanthionyl, and the like, and modifications 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.

[0068] "Hydroxyl" means --OH.

[0069] "Imino" means -NR-, where R can be H or optionally substituted alkyl.

[0070] "Oxo" means the group ═O.

[0071] "Oxy" means --O--.

[0072] As used herein, the term "about" means ±10% of any recited value. As used herein, the term modifies any recited value, range of values, or one or more of the endpoints of a range.

[0073] 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.

[0074] Other features and advantages of the invention will become apparent from the following description and from the claims. [Brief description of the drawings]

[0075] [Figure 1A] Figure 1 shows non-limiting methods using organometallic precursors and organic co-reactants: (A) A first method 100 is shown to provide either a positive resist (path i) or a negative resist (path ii). [Figure 1B] 1A-1D show non-limiting methods using organometallic precursors and organic co-reactants.(B) A block diagram of an exemplary method 150 is shown. [Figure 1C] (C) A graph showing the effect of non-limiting post-exposure incubation conditions (100° C., 150° C., or 175° C. for 2 minutes) using water as the developer. [Figure 1D] (D) A graph showing the effect of non-limiting post-exposure incubation conditions (100° C., 150° C., or 200° C. for 2 minutes, or 150° C. for 2 minutes with a 4 day delay before development begins) using 2-heptanone as the developer. [Figure 1E] (E) A graph showing the effect of non-limiting post-exposure incubation conditions (150° C. for 2 minutes) using water alone, isopropyl alcohol (IPA) alone, or a 1:1 mixture of water and IPA.

[0076] [Figure 2A] Schematic diagrams showing exemplary organometallic precursors and organic co-reactants for depositing modified precursors: (A) A Sn(IV) organometallic precursor (I-1) is shown in the presence of a first organic co-reactant (C-1). [Figure 2B] Schematic diagrams showing exemplary organometallic precursors and organic co-reactants for depositing modified precursors: (A) Sn(IV) organometallic precursor (I-1) in the presence of a second organic co-reactant (C-2). [Figure 2C]Schematic diagram showing exemplary organometallic precursors and organic co-reactants for depositing modified precursors. (C) Different Sn(IV) organometallic precursors (I-2) are shown in the presence of a first organic co-reactant (C-1). [Figure 2D] Schematic diagram showing exemplary organometallic precursors and organic co-reactants for depositing modified precursors. (D) A different Sn(IV) organometallic precursor (I-2) is shown in the presence of a second organic co-reactant (C-2). [Figure 2E] Schematic diagram showing exemplary organometallic precursors and organic co-reactants for depositing modified precursors: (E) Sn(II) organometallic precursor (I-3) is shown in the presence of a first organic co-reactant (C-1). [Figure 2F] Schematic diagram showing exemplary organometallic precursors and organic co-reactants for depositing modified precursors. (F) A Sn(II) organometallic precursor (I-3) is shown in the presence of a first organic co-reactant (C-1) and a tellurium-containing precursor (TeR2). [Figure 2G] Schematic diagram showing exemplary organometallic precursors and organic co-reactants for depositing modified precursors. (G) Another Sn(II) organometallic precursor (I-4) is shown in the presence of a second organic co-reactant (C-2). [Figure 2H] Schematic diagram of exemplary organometallic precursors and organic co-reactants for depositing modified precursors. (H) Shown is a Sn(II) organometallic precursor (I-4) in the presence of a third organic co-reactant (C-3).

[0077] [Figure 3A] Non-limiting scanning electron microscope (SEM) images of resist films with half pitch (HP) 14 nm (HP14). (A) A resist film is shown deposited using a first tin-containing precursor containing a methyl group, a second tin-containing precursor containing an isopropyl group, and acetone as an organic co-reactant. EUV patterning was performed at PSI, Switzerland. [Figure 3B](A) Non-limiting scanning electron microscope (SEM) images of resist films with half pitch (HP) 14 nm (HP14). (B) Resist films deposited using a first tin-containing precursor with a methyl group and acetone as an organic co-reactant are shown. EUV patterning was performed at PSI, Switzerland.

[0078] [Figure 4A] Schematic diagrams illustrating exemplary stacks: (A) A stack is shown including a film 402 deposited with a modified precursor. [Figure 4B] Schematic diagrams showing an exemplary stack (A) and (B) another stack is shown including a film 412 with different carbon content in regions 412a, 412b by controlling the amount of organometallic precursor and organic co-reactant. [Figure 4C] Schematic diagrams illustrating an exemplary stack (C) yet another stack including a modified precursor-deposited film 423, where the film 423 is a capping layer disposed on a photoresist layer 422.

[0079] [Diagram 5] FIG. 5 is a schematic diagram illustrating one embodiment of a process station 500 for dry development.

[0080] [Figure 6] FIG. 6 is a schematic diagram illustrating one embodiment of a multi-station processing tool 600.

[0081] [Figure 7] FIG. 7 is a schematic diagram illustrating one embodiment of an inductively coupled plasma device 700.

[0082] [Figure 8] FIG. 8 is a schematic diagram illustrating an embodiment of a semiconductor process cluster tool architecture 800. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0083] The present disclosure generally relates to the field of semiconductor processing. In particular, the present disclosure is directed to the use of one or more organometallic precursors in combination with one or more organic co-reactants, thereby resulting in a modified precursor for deposition. Such modified precursors may include the metal center of the organometallic precursor and the organic moiety of the organic co-reactant. In this manner, the chemical, physical, and / or optical properties of the deposited film can be controlled by controlling the extent of reaction of the organometallic precursor with the organic co-reactant, by selecting the appropriate combination of moieties and ligands present in the precursor and co-reactant, and / or by determining the desired amount of precursor and co-reactant to introduce during deposition. Further enhancement of the film's properties can be obtained by incubating the film after exposure. As described herein, such modified precursors can provide a film that can be incubated and developed to further enhance the material difference between exposed and unexposed regions.

[0084] Reference will be made in detail 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 in order not to unnecessarily obscure the present disclosure.

[0085] EUV lithography utilizes 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) that is produced by a liquid-based spin-on technique. An alternative to CAR is a direct photopatternable metal oxide-containing film, such as those available from Inpria Corp. (Corvallis, Oregon), and described in, for example, U.S. Patent Application Publication No. 2017 / 0102612, U.S. Patent Application Publication No. 2016 / 0216606, and U.S. 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 produced by spin-on techniques or dry vapor deposition. The metal oxide-containing films can be directly patterned (i.e., without the use of a separate photoresist) by EUV exposure in a vacuum atmosphere resulting in 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 directly 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.

[0086] Directly photopatternable EUV or DUV resists may be composed of or include metals and / or metal oxides mixed within an organic component. The metals / metal oxides may enhance EUV or DUV photon adsorption, generate secondary electrons, and / or exhibit increased etch selectivity relative to the underlying film stack and device layers. These resists can be 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. Such resists can also be developed using a dry approach, or a combination of wet and dry approaches, as described herein.

[0087] 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.

[0088] It would also be beneficial to have a resist that allows post-exposure incubation and development conditions to tailor the DtG or DtC or DtS properties of the film. In certain embodiments, DtC is considered to be the exposure dose that, upon development, results in removal of the exposed photoresist regions (e.g., in the case of a positive resist). Such removal can be quantified in any useful manner, such as a change in thickness of the exposed regions (e.g., a loss of a certain thickness). In other embodiments, DtG is considered to be the exposure dose that, upon development, results in insolubilization of the exposed photoresist regions (e.g., in the case of a negative resist). Such insolubility can be quantified in any useful manner, such as a change in thickness of the exposed regions (e.g., an increase of a certain thickness). In yet other embodiments, DtS is considered to be the exposure dose that, upon development, results in a particular dimension of the exposed photoresist regions.

[0089] The present disclosure generally includes any useful method using a film formed from a modified precursor, which is further incubated to enhance the material difference between exposed and unexposed regions, and then developed to remove either the exposed or unexposed regions. Such methods may include any useful lithography process, deposition process, radiation exposure process, development process, and post-application process described herein. In some embodiments, either a positive resist or a negative resist can be provided by selecting an organic co-reactant. Thus, the methods herein also include methods using a positive resist or a negative resist. The development of the positive resist or the negative resist may include wet development, dry development, or a combination thereof.

[0090] Below, techniques related to EUV processes may be described, but such techniques may also be applicable to other next generation lithography techniques. A variety of radiation sources may 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).

[0091] FIG. 1A illustrates an exemplary method 100 as a schematic diagram, and FIG. 1B illustrates an exemplary method 150 as a flow chart. Turning to FIG. 1A, the exemplary method 100 may include providing an organometallic precursor 10 in the presence of an organic co-reactant 12 (e.g., any described herein). In particular, the organic co-reactant replaces at least one ligand in the organometallic precursor to provide a modified precursor. The method 100 further includes depositing 101 the modified precursor as a film 112 on an upper surface of a substrate 111, the film 112 including an EUV-sensitive material. The deposition may include the use of a corresponding reactant, such as any described herein (e.g., water vapor).

[0092] The composition of the film is determined by the organometallic precursor, organic co-reactant, and the corresponding reactant used during deposition. Non-limiting films include organotin acetylide oxides (e.g., using an organotin precursor, an acetylene-containing co-reactant, and an optional oxygen-containing corresponding reactant), tin acetylide oxides (e.g., using an organotin precursor, an acetylene-containing co-reactant, and an optional oxygen-containing corresponding reactant), tin acetylide tellurides (e.g., using an organotin precursor, an acetylene-containing co-reactant, and a tellurium-containing corresponding reactant), organotin oxalates (e.g., using an organotin precursor, an oxalyl-containing co-reactant, and an optional oxygen-containing corresponding reactant), tin oxalates (e.g., using an organotin precursor, an oxalyl-containing co-reactant, and an optional oxygen-containing corresponding reactant), and tin oxalates (e.g., using an organotin precursor, an oxalyl-containing co-reactant, and an optional oxygen-containing corresponding reactant). reactant, and an optional oxygen-containing corresponding reactant), organotin formates (e.g., using an organotin precursor, a monocarboxylic acid-containing co-reactant, and an optional oxygen-containing corresponding reactant), tin formates (e.g., using an organotin precursor, a monocarboxylic acid-containing co-reactant, and an optional oxygen-containing corresponding reactant), organotin peroxides (e.g., using an organotin precursor, a peroxo-containing co-reactant, and an optional oxygen-containing corresponding reactant), or tin peroxides (e.g., using an organotin precursor, a peroxo-containing co-reactant, and an optional oxygen-containing corresponding reactant).

[0093] The method may further include a step of treating the deposited EUV sensitive film. Such a step is not necessary to form the film, but may be useful for using the film as a PR. Thus, the method 100 further includes patterning the film with an EUV exposure 102 to provide an exposed film having EUV exposed regions 112b and EUV non-exposed regions 112c. The patterning may include the use of a mask 114 having EUV transparent and EUV opaque regions, where an EUV beam 115 is transmitted through the EUV transparent regions to the film 112. 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). In certain embodiments, the radiation dose is about 1 to 50 mJ / cm. 2 In another embodiment, the radiation dose is about 1 to 10 mJ / cm.2 , 1~20mJ / cm 2 , 1~30mJ / cm 2 , 1~40mJ / cm 2 , 10~20mJ / cm 2 , 10~30mJ / cm 2 , 10~40mJ / cm 2 , or 10-50mJ / cm 2 It is.

[0094] Once the pattern is provided, the method 100 may include incubating 103 the film to further differentiate one or more material properties between the exposed and unexposed regions, thereby providing an incubated film having incubated exposed regions 112d and incubated unexposed regions 112e. Without wishing to be limited by mechanism, the incubation may promote certain chemical or physical processes in the exposed and unexposed regions to further differentiate the solubility of the material in those regions upon exposure to a developer. As one non-limiting example, incubation may result in a low level of crosslinking in the unexposed regions and a high level of crosslinking in the exposed regions, thereby rendering the exposed regions resistant to dissolution in the developer. The degree of crosslinking may be affected by the degree of moisture loss, thermal decomposition of tin-organic moieties, and / or loss of organic ligands in certain regions. Such crosslinking may include the formation of metal-oxygen bonds, metal-carbon bonds, or carbon-carbon bonds (e.g., between ligands).

[0095] Incubation conditions may include incubating the exposed film at a temperature of about 20-300° C. In one example, incubating the exposed film at a temperature of about 100-250° C. in an ambient atmosphere increases the material difference between exposed and unexposed regions. This difference can be used to enhance DtG or DtC or DtS when developed with a particular developer (e.g., aqueous developer, gaseous water, or halide vapor). Such incubation for the film may include a time of about 30-300 seconds.

[0096] In another example, the exposed film is incubated at a low temperature of about 20-30° C. for an extended period of time (e.g., 1-7 days) to increase the material difference between exposed and unexposed regions. This difference can be used to enhance DtG or DtC or DtS when developed in a particular developer (e.g., aqueous developer, organic developer, or combinations thereof, and any of those described herein). Such incubation can be performed in ambient atmosphere (e.g., ambient air), or, as described below, nitrogen (N 2 ), oxygen (O 2 ), water vapor (H 2 O), carbon dioxide (CO 2 ), carbon monoxide (CO), argon (Ar), helium (He), or other atmospheres having one or more of these combinations.

[0097] In certain examples, exposure to high temperatures (e.g., above 200° C., 250° C., or higher) can render the entire film insoluble, thus losing the patterning resolution provided by the radiation exposure. However, high temperatures can be used under controlled atmospheric conditions. Thus, in one example, incubating the exposed film at elevated temperatures of about 150-300° C. in an inert atmosphere increases the material difference between exposed and unexposed regions. This difference can be used to enhance DtG or DtC or DtS when developed with a particular developer (e.g., aqueous developer, organic developer, or combinations thereof, and any described herein). Such incubations may include times of about 1-300 seconds. Optionally, some moisture may be present. Such incubations may be performed in the following manner: nitrogen (N 2 ), oxygen (O 2 ), water vapor (H 2 O), carbon dioxide (CO 2 The reaction can be carried out in an atmosphere having one or more of: nitrogen, carbon monoxide (CO), argon (Ar), helium (He), or a combination thereof.

[0098] Thus, in one example, the incubated membrane may include regions of enhanced hydrophobicity / hydrophilicity differences between incubated exposed and non-exposed regions. Such differences can be enhanced by hydrophilic conditions (e.g., aqueous developers, alcohols, acids, bases, gaseous water, oxygen (O 2 It may be advantageous in that more hydrophilic regions can be removed using hydrophobic conditions (e.g., ketones, esters, alcohols, ethers, or combinations thereof) and more hydrophobic regions can be removed using hydrophobic conditions (e.g., ketones, esters, alcohols, ethers, or combinations thereof). In any of these embodiments, wet or dry development conditions can be used. In certain instances, developing includes a wet development process in conjunction with a dry development process. Such processes include the use of gases such as water, oxygen (O 2 ), gases including gaseous acids, gaseous halides, or combinations thereof, along with ketones or liquid water.

[0099] Returning to Figure 1A, method 100 may include developing 104 the incubated film, which may either (i) remove the EUV exposed regions to provide a pattern in the positive resist film, or (ii) remove the EUV non-exposed regions to provide a pattern in the negative resist. Path (i) in Figure 1A results in selective removal of EUV exposed and incubated regions 112d, which may be facilitated by using organic co-reactants that provide binding ligands that are less stable after EUV exposure (e.g., that release gaseous by-products upon exposure to EUV radiation) and / or by using incubation conditions such that EUV exposed and incubated regions 112d are more readily dissolved by a developer and / or by using incubation conditions such that EUV non-exposed and incubated regions 112e are less readily dissolved by a developer. Alternatively, route (ii) of FIG. 1A results in maintaining the EUV exposed and incubated region 112d, which may be facilitated by using an organic co-reactant that results in a bound ligand that is more stable after EUV exposure (e.g., less susceptible to development after EUV exposure) and / or by using incubation conditions such that the EUV exposed and incubated region 112d is less easily dissolved by a developer and / or by using incubation conditions such that the EUV non-exposed region and incubated 112e are more easily dissolved by a developer.

[0100] The development step may include the use of water vapor or halide chemicals (e.g., HBr chemicals) in the gas phase, or aqueous or organic solvents in the liquid phase, and combinations thereof. In certain examples, wet development is used, such as using water, acids, bases, ketones, esters, alcohols, ethers, surfactants, or combinations thereof for an optional time of about 15-120 seconds. In other examples, dry development is used alone or in combination with wet development (e.g., as a sequential step). Dry development may include, for example, gaseous water, oxygen (O), at an optional pressure of about 0.1-1 Torr for an optional time of about 30-720 seconds.2 ), gaseous acid, gaseous halide, or a combination thereof (e.g., water containing an acid, or O containing an acid 2 ).

[0101] The development step may include any useful experimental conditions, such as low pressure conditions (e.g., about 1-100 mTorr), plasma exposure (e.g., in the presence of a vacuum), and / or thermal conditions (e.g., about -10 to 100 °C) that can be combined with any useful chemicals (e.g., halide chemicals or aqueous chemicals). Development can be performed using, for example, hydrochloric acid (HCl), hydrobromic acid (HBr), hydrogen gas (H 2 ), chlorine gas (Cl 2 ), bromine gas (Br 2 ), boron trichloride (BCl 3 ), or a combination thereof, as well as any of the halide-based developing processes described herein, aqueous alkaline developing solutions, or organic developing solutions. Additional developing process conditions are described herein.

[0102] 1C-1E show non-limiting film results. The films comprise an organotin-based photoresist that was exposed to various radiation doses, incubated for 2 minutes at the indicated temperature, developed in the indicated developer for 10 seconds, and then rinsed for 10 seconds (in the same solvent as the developer). After development, the film thickness was measured for each exposure dose.

[0103] Figure 1C shows the effect of different incubation temperatures on films developed using water (as the developer). As shown, incubating the exposed film at 175 °C reduces the amount of photoinduced ... 2 ) with improved DtG (3mJ / cm 2 ).

[0104] Figure 1D shows the use of 2-heptanone as the developer. As can be seen, increasing the incubation temperature increased the DtG under the conditions tested. Delaying development (4 days) after incubation at 150 °C improved the DtG (15 mJ / cm 2 (See below). Figure 1E shows the use of isopropanol (IPA), water, or a mixture of IPA and water as the developer. While not wishing to be limited by mechanism, such solvent studies can be used to more fully elucidate the mechanism of film dissolution and to control the solubility of the various components of the film.

[0105] Optional steps can be performed to further condition, modify, or process the EUV sensitive film, substrate, photoresist layer, and / or any of the methods herein. FIG. 1B shows a flow chart of an exemplary method 150 having various operations, including optional operations. As shown, in operation 152, an organometallic precursor is provided in the presence of an organic co-reactant, resulting in a modified precursor (e.g., in a chamber). In operation 154, a film is deposited using the modified precursor. Operation 156 is then an optional process of modifying the amount of organometallic precursor and organic co-reactant, thereby resulting in an additional modified precursor. Such modification may include increasing or decreasing the amount of organometallic precursor and / or organic co-reactant. Optional operation 158 includes depositing an additional modified precursor. Operations 156, 158 can be repeated as desired to form a film having a modified precursor.

[0106] In operation 160, 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 be provided with a positive tone resist or a negative tone resist as described herein.

[0107] In operation 162, the exposed film is incubated to further increase the contrast in the etch selectivity of the exposed film. In one example, the exposed film can be incubated at a temperature of about 20-300° C. For example, incubations can include long periods at low temperatures (e.g., greater than 1 day at about 20-30° C. or 20-35° C.), short periods at intermediate temperatures (e.g., less than 10 minutes at about 100-200° C. or 150-200° C.), or short periods at high temperatures (e.g., less than 10 minutes at about 100-300° C., 150-300° C., or 200-300° C.). Such incubations (e.g., optionally in the presence of various chemical species) can include, but are not limited to, a stripping agent (e.g., an aqueous developer solution; gaseous water; oxygen (O 2 ); gaseous acids; gaseous halides; halide-based etchants, e.g., HCl, HBr, H 2 , Cl 2 , Br 2 , BCl 3 or a combination thereof, and any halide-based development process described herein; an organic developer solution; or others described herein), can promote reactivity in the EUV-exposed or EUV-unexposed regions of the resist. In some embodiments, the exposed film can be thermally treated to further crosslink ligands in the EUV-exposed portions of the resist, thereby providing EUV-unexposed portions that can be selectively removed upon exposure to a stripper (e.g., a negative tone developer).

[0108] The PR pattern is then developed in operation 164. 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. The dry process may include a gas (e.g., including water, oxygen, acid, halide, or combinations thereof) at a pressure of about 0.1-1 Torr for a time of about 30-720 seconds. The wet process may include a liquid (e.g., water, acid, base, ketone, ester, alcohol, ether, or combinations thereof) at room temperature (e.g., about 20-30° C. or 20-25° C.) for a time of about 15-60 seconds. In one example, these steps may include a wet process followed by a dry process in any order. Such processes may be performed in cycles (e.g., n cycles of alternating wet and dry processes (n can be 1, 2, 3, 4, 5, or more)).

[0109] Other optional steps may be performed. Optionally, the method may include cleaning the backside or bevel of the substrate (e.g., after deposition) or removing the edge bead of a deposition film deposited in a previous step. Such cleaning or removal steps may be useful to remove particles that may be present after depositing a film layer. The removal step may be performed using a wet metal oxide (MeO x ) treating the wafer with an edge bead removal (EBR) process.

[0110] In another example, the method may include an optional step of performing a post application bake (PAB) of the deposited film to remove residual moisture or pretreat the deposited film in any useful manner. The optional PAB can be performed after film deposition and before 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 the pattern in the film. In certain embodiments, the PAB step is performed at a temperature above about 100° C., or at a temperature between about 100 and 200° C., or between about 100 and 250° C. In some cases, the PAB is not performed within the method.

[0111] In yet another example, the method may include the optional step of performing a post-exposure bake (PEB) of the exposed film to further remove residual moisture, promote chemical condensation within the film, or post-treat the film in any useful manner. In another example, the method may include hardening the patterned film (e.g., after development) to thereby provide a resist mask disposed on top of the substrate. The hardening step may include any useful process, such as a plasma (e.g., O 2 ), that further crosslinks or reacts the EUV unexposed or EUV exposed regions. 2 , Ar, He, or CO 2 The process may include steps such as exposure to a plasma, exposure to ultraviolet radiation, annealing (e.g., at a temperature of about 180-240° 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 may be performed as optional steps in any of the methods described herein.

[0112] 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 liquid 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 photoresists (wet processes) such as those available from Inpria Corp., 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.

[0113] In some embodiments, dry processes are used. For example, dry vapor deposition techniques described herein can be used to deposit thin, defect-free films, and the exact thickness of the deposited film can be adjusted and controlled by increasing or decreasing the length of the deposition step or sequence. Thus, dry processes can provide tunability and critical dimension (CD) control and scum removal. Dry development can provide improved performance (e.g., prevention of line collapse), improved throughput, reduced susceptibility to adhesion problems, improved line edge roughness, enable direct patterning on device topography, and / or the ability to tailor hardmask chemistry to specific substrates and semiconductor device designs. In other embodiments, a combination of wet and dry processes (e.g., processes such as deposition, development, or other processing operations) is used to provide such benefits. In still other embodiments, wet processes (e.g., processes such as deposition, development, or other processing operations) are used to provide such benefits. Additional details, materials, processes, steps, and apparatus are described herein.

[0114] Modified Precursor The present disclosure relates to the use of organometallic precursors in the presence of organic co-reactants to generate modified precursors that are then readily deposited to form patterned radiation-sensitive films (e.g., EUV-sensitive films). The films can then function as EUV resists, as described further herein. In certain embodiments, the modified precursors are generated and deposited in situ, e.g., generation occurs within the chamber for deposition.

[0115] The modified precursor may be a reaction product formed between an organometallic precursor and an organic co-reactant, which reaction product may then be deposited to form a film. Such reaction and deposition may be carried out in vapor form or in solvent (or liquid) form. In certain embodiments, the film may include one or more ligands (e.g., labile ligands) that may be removed, cleaved, or crosslinked by radiation (e.g., EUV or DUV radiation).

[0116] In some embodiments, the use of carbon-containing co-reactants (or organic co-reactants) can expand the library of film compositions and allow for tuning of films for various properties (e.g., film mechanical properties, optical properties such as patterning radiation sensitivity, and / or patterning performance). Such organic co-reactants can be used during the deposition process to separate the density of radiation sensitive elements and the density of radiation responsive organic moieties in the film, thereby tuning the ratio of radiation sensitive metal to radiation responsive organic moieties, which may result in improved patterning radiation sensitivity and / or improved resulting patterning quality.

[0117] Additionally, the organic co-reactant can be selected to impart other beneficial properties to the film. In one example, the selected organic co-reactant can introduce ligands to the metal centers of the precursor that become highly soluble in positive tone developers upon exposure to patterning radiation. Exemplary ligands include divalent oxalyl ligands located between the metal centers that provide a resilient film in radiation unexposed areas (e.g., EUV or DUV unexposed areas) but result in a removable film in radiation exposed areas (e.g., EUV or DUV exposed areas). In this way, the organic co-reactant can provide a positive tone resist. In another example, the introduced ligands include polymerizable moieties (e.g., alkenylene, alkynylene, or epoxy) located between the metal centers that can undergo photopolymerization in radiation exposed areas. In this way, the organic co-reactant strengthens the negative tone resist.

[0118] The organometallic precursor can include any precursor (e.g., as described herein) that provides a patternable film (or a patterned radiation-sensitive film or a photopatternable film) that is radiation sensitive. Such radiation can include EUV or DUV radiation provided by irradiating through a patterning mask, thereby providing the patterning radiation. The film itself can be altered by exposure to such radiation such that it becomes radiation sensitive. In certain embodiments, the organometallic precursor is an organometallic compound that includes at least one metal center and at least one ligand capable of reacting with an organic co-reactant. In this manner, the organic moiety of the co-reactant reacts with or replaces the ligand of the metal center, thereby attaching the organic moiety to the metal center as a binding ligand. The organic moiety can itself increase the EUV / DUV sensitivity of the film (e.g., by increasing the EUV / DUV absorptivity) or increase the contrast selectivity during development (e.g., by increasing the porosity of the film). Additionally, the organic moieties may be reactive in the presence of the patterning radiation, for example by undergoing removal or desorption from the metal center, or by reacting or polymerizing with other moieties within the film.

[0119] The organometallic precursor can have any useful number and type of ligands. As discussed herein, at least one ligand reacts with an organic co-reactant. The ligand can also be characterized by its ability to react in the presence of a corresponding reactant or in the presence of patterning radiation. For example, the organometallic precursor can include a ligand that reacts with a corresponding reactant that can introduce a bond (e.g., an -O- bond) between the metal centers. Such a ligand (e.g., a dialkylamino group or an alkoxy group) can also react with an organic co-reactant in some cases. In another example, the organometallic precursor can include a ligand that leaves in the presence of patterning radiation. Such a ligand can include a branched or linear alkyl group with a β-hydrogen.

[0120] The organometallic precursor can be any useful metal-containing precursor, such as an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In a non-limiting example, the organometallic precursor has the formula (I): M a R b L c (I) (wherein 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 reactive with an organic co-reactant or counter reactant, and R and L together with M can optionally form a heterocyclyl group, or R and L together can optionally form a heterocyclyl group; a ≧1, b ≧1, and c ≧1.

[0121] In some embodiments, each ligand in the organometallic precursor can be a ligand that is reactive with an organic co-reactant or a corresponding reactant. In one example, the organometallic precursor comprises a structure having formula (I), where each R is independently L. In another example, the organometallic precursor comprises a structure having formula (Ia): M a L c (Ia) (wherein M is a metal or metalloid; each L is independently a ligand, an ion, or other moiety reactive with an organic co-reactant or counter reactant, and two L's together can optionally form a heterocyclyl group; a >= 1 and c >= 1. In certain embodiments of Formula (Ia), a is 1. In further embodiments, c is 2, 3, or 4.

[0122] For any formula herein, M is the large patterning radiation absorption cross section (e.g., 1×10 7 cm 2M may be a metal or metalloid having an EUV absorption cross section equal to or greater than 1000 nm / mol. In some embodiments, M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), hafnium (Hf), or zirconium (Zr). In further embodiments, in formula (I) or (Ia), M is Sn, a is 1, and c is 4. In other embodiments, in formula (I) or (Ia), M is Sn, a is 1, and c is 2. In certain embodiments, M is Sn(II) (e.g., in formula (I) or (Ia)), thereby resulting in an organometallic precursor that is a Sn(II)-based compound. In other embodiments, M is Sn(IV) (e.g., in formula (I) or (Ia)), thereby resulting in an organometallic precursor that is a Sn(IV)-based compound.

[0123] 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, the 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, the optionally substituted bis(trialkylsilyl)amino is -N(SiR 1 R 2 R 3 ) 2 And each R 1 , R 2 , and R 3is 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.

[0124] 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 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 taken together with the oxygen atom and metal atom to which each is attached form a heterocyclyl group, as defined herein.

[0125] In some embodiments, at least one of L or R is an optionally substituted alkyl (e.g., in formula (I) or (Ia)). 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 β hydrogen or β fluorine. In particular, the organometallic precursor is tetramethyltin (SnMe 4 ), tetraethyltin (SnEt 4), t-Butyl tellurium hydride (Te(t-Bu)(H)), dimethyl tellurium (TeMe 2 ), di(t-butyl)tellurium (Te(t-Bu) 2 ), or di(isopropyl)tellurium (Te(i-Pr) 2 ).

[0126] In some embodiments, each L or at least one L is halo (e.g., in formula (I) or (Ia)). In particular, the organometallic precursor can be a metal halide. Non-limiting metal halides include SnBr 4 , SnCl 4 , SnI 4 , and SbCl 3 Examples include:

[0127] In some embodiments, each L or at least one L may include a nitrogen atom. In certain embodiments, one or more L may be an optionally substituted amino or an optionally substituted bis(trialkylsilyl)amino (e.g., in formula (I) or (Ia)). Non-limiting L substituents include, for example, -NMe 2 , -NEt 2 , -NMeEt, -N(t-Bu)-[CHCH 3 ] 2 -N(t-Bu)-(tbba), -N(SiMe 3 ) 2 , and -N(SiEt 3 ) 2 Non-limiting examples of organometallic precursors include Sn(NMe 2 ) 4 , Sn(NEt 2 ) 4 , Sn(i-Pr)(NMe 2 ) 3 , Sn(n-Bu)(NMe 2 ) 3 , Sn(s-Bu)(NMe 2 ) 3 , Sn(i-Bu)(NMe 2 ) 3 , Sn(t-Bu)(NMe 2 )3 , Sn(t-Bu) 2 (NMe 2 ) 2 , Sn(t-Bu)(NEt 2 ) 3 , Sb(NMe 2 ) 3 , Sn(tbba), Sn[N(SiMe 3 ) 2 ] 2 , or Bi[N(SiMe 3 ) 2 ] 3 The following can be mentioned.

[0128] In some embodiments, each L or at least one L may include a silicon atom. In certain embodiments, one or more L may be an optionally substituted trialkylsilyl or an optionally substituted bis(trialkylsilyl)amino (e.g., in formula (I) or (Ia)). Non-limiting L substituents include, for example, -SiMe 3 , -SiEt 3 , -N(SiMe 3 ) 2 , and -N(SiEt 3 ) 2 Non-limiting examples of organometallic precursors include Sn[N(SiMe 3 ) 2 ] 2 , bis(trimethylsilyl)tellurium (Te(SiMe 3 ) 2 ), bis(triethylsilyl)tellurium (Te(SiEt 3 ) 2 ), or Bi[N(SiMe 3 ) 2 ] 3 Examples include:

[0129] In some embodiments, each L or at least one L may include an oxygen atom. In certain embodiments, one or more L may be an optionally substituted alkoxy (e.g., in formula (I) or (Ia)). Non-limiting L substituents include, for example, methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), and -O=C(CH 3 )-CH=C(CH 3 )-O-(acac). Non-limiting examples of organometallic precursors include Sn(t-BuO) 4 , Sn(n-Bu)(t-BuO) 3 , or Sn(acac) 2 Examples include:

[0130] Further, other organometallic precursors and non-limiting substituents are described herein.For example, the organometallic precursor can be any of the structures of formula (I) and (Ia) above, or formula (III), (IV), (V), (VI), (VII), or (VIII) described below.Any of the substituents M, R, X, or L described herein can be used in any of formulas (I), (Ia), (III), (IV), (V), (VI), (VII), or (VIII).

[0131] An organic co-reactant is used to react with or replace the ligands of the organometallic precursor to provide the modified precursor. Any useful organic co-reactant can be used. Such organic co-reactants can be provided in any form, for example, in the gas phase.

[0132] In one non-limiting example, the organic co-reactant has the formula (II): X 1 -ZX 2 (II) (In the formula, X 1 and X 2 each is independently a leaving group (e.g., halo, H, hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, etc.); Z is a compound having a carbonyl, dicarbonyl, optionally substituted alkylene, optionally substituted haloalkylene, optionally substituted alkenylene, or optionally substituted alkynylene.

[0133] In some embodiments, Z is substituted with one or more oxo (=O) groups. In certain embodiments, Z is oxalyl, methoxalyl, malonyl, or oxalacetyl. In other embodiments, Z contains one or more saturated bonds. In certain embodiments, Z is ethynylene. Examples of organic co-reactants include oxalyl chloride, acetylene, and the like, and derivatives thereof. In other embodiments, Z is substituted with one or more halo groups.

[0134] In some embodiments, the organic co-reactant has the formula (IIa): X 1 -C≡CH(IIa) (In the formula, X 1 is a leaving group such as halo, H, or optionally substituted alkyl.

[0135] In other embodiments, the organic co-reactant has the formula (IIb): X 1 -C(O)-X 2 (IIb) (In the formula, X 1 and X 2 Each of is independently a leaving group such as halo, H, hydroxyl, optionally substituted alkyl, or optionally substituted alkoxy), a carbonyl-containing derivative having a substituted or unsubstituted aryl group.

[0136] In other embodiments, the organic co-reactant has the formula (IIc): X 1 -C(O)-C(O)-X 2 (IIc) (In the formula, X 1 and X 2Each of is independently an oxalyl derivative having a leaving group such as halo, H, hydroxyl, optionally substituted alkyl, or optionally substituted alkoxy.

[0137] In yet other embodiments, the organic co-reactant has the formula (IId): X 1 -Ak-H(IId) (In the formula, X 1 is a leaving group such as halo, hydroxyl, optionally substituted alkyl, or optionally substituted alkoxy; Ak is an alkyl derivative having an optionally substituted alkylene or an optionally substituted haloalkylene. When at least one halo is present, then the organic co-reactant can be a haloalkyl moiety or a haloalkyl derivative. In certain embodiments, the organic co-reactant is a haloalkyl derivative (e.g., where the halo is iodo) and the organometallic precursor is a Sn(II)-based compound.

[0138] Without wishing to be limited by mechanism, modified precursors obtained using such compounds may involve the oxidative addition of low-valent Sn(II) species or other electron-rich metal precursors to interact with reactive carbon-halogen bonds of added organic co-reactants (e.g., provided in the gas phase). In some examples, the reactive carbon-halogen bonds are reactive carbon-iodine bonds. Non-limiting alkyl derivatives include ethyl iodide, isopropyl iodide, t-butyl iodide, diiodomethane, and the like.

[0139] In some cases, the electron rich metal precursor is a trivalent Sb or Bi precursor. Non-limiting precursors include SbR 3 or BiR 3 (For example, R can be any of those described herein, such as those in formula (I), (IV), or (VI)), to which an alkyl halide can be added to form a pentavalent complex. In particular, Sb and Bi are of interest due to their large EUV absorption cross sections.

[0140] The method can also employ a chalcogenide precursor as a counter reactant or an organic co-reactant. In certain embodiments, the chalcogenide precursor has the formula (IIe): X 3 -ZX 4 (No) (wherein Z is sulfur, selenium, or tellurium; X 3 and X 4 each of which 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.

[0141] An organic co-reactant can be used to replace at least one ligand of the organometallic precursor, where the organic co-reactant provides a binding ligand to the modified precursor. In one example, the organic co-reactant can include a structure having formula (II), where the binding ligand can include or be any useful substituent resulting from the reaction of the organometallic precursor with the organic co-reactant (optionally with a corresponding reactant). In certain embodiments, the binding ligand in the modified precursor is -X a -ZX b -, Z may be an optionally substituted alkylene, an optionally substituted alkenylene, or an optionally substituted alkynylene (e.g., ethynylene, oxalyl, methoxalyl, malonyl, or oxalacetyl), and X a and X b Each of -X is independently a bond (e.g., a covalent bond), an oxy, an imino, or a carbonyl. a -ZX cwherein Z is an optionally substituted alkylene, an optionally substituted alkenylene, or an optionally substituted alkynylene (e.g., ethynylene, oxalyl, methoxalyl, malonyl, or oxalacetyl), and X a are independently a bond (e.g., a covalent bond), oxy, imino, or carbonyl; X c is halo, H, hydroxyl, optionally substituted alkyl, or optionally substituted alkoxy.

[0142] In some embodiments, the organic co-reactant includes one or more bulky substituents, thereby resulting in a modified precursor having a bound ligand that includes a bulky substituent. In one example, the bulky organic co-reactant can increase the dry development contrast of the film due to an increase in the difference in porosity between radiation-exposed and non-exposed regions. In another example, the bulky organic co-reactant can lead to an increase in the dry development rate due to an increase in the difference in porosity between radiation-exposed and non-exposed regions. In general, bulkier substituents can result in a film with increased porosity, which increases access to etchants or development chemicals. Porosity can be characterized in any useful manner, such as, for example, volumetric gas adsorption.

[0143] FIG. 2A illustrates a non-limiting embodiment of an organometallic precursor in the presence of an organic co-reactant. As shown, the non-limiting organometallic precursor can be a tin-based compound (Sn(i-Pr)(NMe) provided in the presence of a non-limiting organic co-reactant, such as acetylene (C-1). 2 ) 3 , I-1). As shown in the figure, the organometallic precursor can be a ligand (e.g., -NMe 2 ), which results in a modified precursor having the formula (II-1a) that can be deposited as a film. As shown, the isopropyl group of the organometallic precursor can be maintained in the modified precursor, and the reactive -NMe 2The ligands can form any useful chemical bond. For example, reactive ligands can react with, for example, an optional oxygen-containing corresponding reactant to provide a terminal -OH moiety or a Sn-O bond, and reactive ligands can react with an organic co-reactant to provide a bound ligand (herein, in formula (II-1a), the bound ligand is -C≡CH).

[0144] As shown, the modified precursor may include any useful chemical bonds within the film, including, but not limited to, a terminal -OH moiety (e.g., as a result of reaction with one or more corresponding reactants), one or more metal-oxygen-metal (MOM) bonds that may be formed between the metal centers of the precursor, one or more bonds that result in a metal-carbon (MC) bond between the metal center and an atom in a binding ligand provided by an organic co-reactant, and / or one or more bonds that result in a metal-oxygen (MO) bond between the metal center and an atom in a binding ligand provided by an organic co-reactant.

[0145] The approach herein can result in improved modified precursors and / or improved films. For example, state-of-the-art metal oxide EUV photoresists are generally generated from organometallic precursors with a highly EUV-sensitive element (e.g., Sn) and an EUV-responsive organic moiety (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc.) directly bonded to the metal center. The precursor is optionally reacted in situ with a corresponding reactant such as water. In this way, the resulting density of EUV-sensitive elements and EUV-sensitive organic moieties is directly coupled by the intrinsic properties of the organometallic precursor. In contrast, the present disclosure allows for tuning the density of EUV-sensitive elements and the density of EUV-responsive organic moieties without the need for modification of the organometallic precursor. In this way, different chemistries can be easily accessed by adjusting the degree of reaction between the organometallic precursor and the organic co-reactant (e.g., by adjusting the amount of organometallic precursor and / or co-reactant, the reaction time between these two compounds, etc.) as well as by separating the density of EUV-sensitive elements from the density of EUV-responsive organic moieties within the film.

[0146] For example, this approach can result in EUV-sensitive films with tunable metal / carbon ratios. In one embodiment, such tuning can result in films with higher EUV responsiveness than currently available photoresists (PR), thus improving wafer patterning throughput. In other embodiments, the process can provide tuning knobs to change dose vs. size, optimize patterning quality (e.g., improve line width roughness (LWR) and / or line edge roughness (LER)), and / or improve mechanical strength. Such tuning can be done between the deposition of two films (e.g., to produce two films with different metal / carbon ratios) or within the same film (e.g., to provide a single film with a gradient of metal / carbon ratios). For example, the approach herein can enable a gradient density of EUV-responsive organic moieties within a film. Without wishing to be limited by mechanism, a gradient density of the EUV sensitive organic moieties may allow for better homogenization of the EUV absorption events, making the development process more reliable and easier to optimize, since more photons are available for absorption near the surface of the PR and fewer reach the bottom.

[0147] In addition, the physical size of the organic co-reactants may result in films with increased porosity in the unexposed regions, which may allow improved diffusion of the gases involved in dry development to the unexposed regions, while reducing the diffusion of the dry development gases in the exposed regions. As a result of this porosity difference, dry development of such films in a negative tone scheme may result in higher contrast between exposed and unexposed regions.

[0148] Furthermore, this approach allows for the provision of films that can be processed with negative tone dry development strategies or positive tone wet development strategies, where the organometallic precursor can be maintained and the organic co-reactant altered to alter the type of film produced. Depending on the chemical structure of the ligand resulting from reacting the organic co-reactant with the organometallic precursor, radiation exposure can stabilize or destabilize the film. As seen in Figure 2A, after depositing the modified precursor, the resulting film can be exposed to EUV radiation. As an example, EUV exposure can result in photopolymerization crosslinking between the bound ethynyl ligands, thereby producing a stabilized crosslinked film (II-1a * ) can be provided. For example, the use of acetylene may result in high performance negative tone patterning as a result of EUV polymerization followed by dry development. In some non-limiting examples, further crosslinking can be obtained in the EUV exposed regions by incubating such films at elevated temperatures (e.g., 100-300°C). Without wishing to be limited by mechanism, such crosslinking may be promoted by increased Sn-O bond formation and / or increased crosslinking between organic ligands. In other examples, incubating such films at elevated temperatures (e.g., 100-300°C) can result in thermal decomposition of ethynyl or ethenyl.

[0149] In another example, radiation exposure can degrade regions in the film, and such modified precursors can provide positive tone photoresists. Figure 2B shows the use of oxalyl chloride (as an organic co-reactant), which may result in high performance positive tone patterning using EUV in a wet development strategy. The inclusion of an oxalyl bridging group can result in unexposed films that are resistant to positive tone wet developers (e.g., tetramethylammonium hydroxide), potentially resulting in high contrast positive tone PR.

[0150] As can be seen in FIG. 2B, non-limiting organometallic precursors (Sn(i-Pr)(NMe 2 ) 3, I-1) in the presence of oxalyl chloride (C-2) to provide a modified precursor having the formula (II-1b). In this modified precursor, the binding ligands include an oxalyl substituent (-C(O)C(O)-) provided by an organic co-reactant and an oxy-substituent (-O-) that may be provided by an oxygen-containing counterpart reactant. Upon exposure to EUV radiation, the binding ligands in the modified precursor are decomposed, thereby providing a metal hydroxide (II-1b * ) and carbon dioxide can be produced. Further treatment of the EUV exposed areas with oxygen provides an additional metal oxide film.

[0151] In some cases, the inclusion of radiation-responsive organic moieties using organic co-reactants may result in films that do not require post-exposure treatment to crosslink metal species. For example, when using oxalyl derivatives, the binding ligands may result in films with oxalyl substituents that do not require post-exposure treatment. Such films may have improved patterning quality (e.g., improved LWR and / or LER) by reducing bake-related haze effects and / or increasing wafer patterning throughput.

[0152] In other examples, the radiation exposed film can be further developed using the development processes described herein. In some embodiments, the film is developed using halide chemicals (e.g., HBr, HCl, and / or BCl 3 ) into a dry-developable solution. In other embodiments, the films can be developed by wet chemistry. For example, but not by way of limitation, the use of oxalyl chloride as an organic co-reactant can provide superior positive wet-developability performance resulting from oxalate bonds between metal centers that are expected to be resistant to positive developers (e.g., aqueous alkaline developers such as tetramethylammonium hydroxide (TMAH), or other wet developers described herein).

[0153] The methods herein also include the use of organometallic precursors that only have ligands that are reactive with the organic co-reactant or the corresponding reactant. In this way, the organic moiety is introduced into the deposited film only through the organic co-reactant. For example, FIG. 2C shows the formation of a metal-organic precursor having a reactive ligand (e.g., -NMe 2 ) alone as organometallic precursor (Sn(NMe 2 ) 4 , I-2), each of which may be reactive with organic co-reactants and / or counter reactants. When used with acetylene (C-1) as the organic co-reactant, the modified precursor (II-2a) may contain bonded ligands (e.g., -C≡CH), hydroxyl moieties, and other metal-oxy bonds. As shown, the carbon content in this film is entirely supplied by the organic co-reactant.

[0154] Upon exposure to patterning radiation, the binding ligands in the modified precursor are crosslinked, thereby forming the structure (II-2a * In another example, FIG. 2D shows a film having an organometallic precursor (Sn(NMe) in the presence of oxalyl chloride (C-2). 2 ) 4 , I-2) and modified precursors (II-2b) containing binding ligands (e.g., -OC(O)C(O)O-), hydroxyl moieties, and other metal-oxy bonds. EUV exposure produces films that release gaseous by-products (e.g., carbon dioxide and / or carbon monoxide) (II-2b). * ) may be provided.

[0155] By decoupling the source of the metal center and the organic moiety, a variety of organometallic precursors can be used. For example, Figures 2E-2H show the use of an organometallic precursor with a tin(II) metal center. As seen in Figure 2E, the organometallic precursor can be used with Sn(II)(tbba) (I-3) in the presence of acetylene (C-1) to yield a modified precursor (II-3a) with photopolymerizable bound ligands, which upon EUV exposure can produce a crosslinked film (II-3a * ) may be provided.

[0156] The organometallic precursor and the organic co-reactant are the chalcogenide precursors (e.g., TeR 2 As seen in Figure 2F, the organometallic precursor of Sn(II)(tbba) (I-3) can be used in the presence of acetylene (C-1) and a Te-containing precursor to yield a modified precursor (II-3b) with photopolymerizable binding ligands and Sn-Te bonds, which upon EUV exposure can produce a crosslinked film (II-3b * Non-limiting Te-containing precursors include any of those described herein, such as TeR 2 where R can be H, optionally substituted alkyl, or optionally substituted trialkylsilyl.

[0157] FIG. 2G illustrates the organometallic precursor (Sn[N(SiMe) 3 ) 2 ] 2 , I-4), which can lead to the modified precursor (II-4a). The resulting film can then be exposed to EUV to form the exposed film (II-4a * ) may be provided.

[0158] Sn(II)-based precursors can be reacted with organic co-reactants to provide Sn(IV)-based modified precursors for deposition. For example, FIG. 2H shows that organometallic precursors (I-4) can be used in the presence of alkyl halides (e.g., isopropyl iodide, C-3) to provide modified precursors (II-5a) with Sn(IV) metal centers. As shown, organic co-reactants can be used in this manner with electron-rich Sn(II) precursors to incorporate EUV-labile alkyl groups (e.g., isopropyl, t-butyl, etc.) and EUV absorption enhancing ligands (e.g., iodide) into the modified precursors. The resulting film can then be treated with an oxygen-containing corresponding reactant to provide an organometallic oxide film (II-5b), which can then be exposed to EUV to provide an exposed film (II-5b). *) to release a cleavable alkyl group (e.g., propylene when the labile alkyl group is isopropyl). The exposed film is then baked to form a metal oxide film (II-5b ** ) may be provided.

[0159] Such EUV absorbing materials and EUV sensitive materials can be deposited in any useful manner described herein.Exemplary deposition techniques include atomic layer deposition (ALD) (e.g., thermal ALD and plasma enhanced ALD (PE-ALD)), spin coat deposition, physical vapor deposition (PVD) including PVD co-sputtering, chemical vapor deposition (CVD), plasma enhanced CVD (PE-CVD), low pressure CVD (LP-CVD), sputter deposition, electron beam (e-beam) deposition including e-beam co-evaporation, etc., or combinations thereof.Other deposition processes and conditions are described herein.

[0160] One or more precursors and one or more organic co-reactants can further be used in any useful combination. For example, different combinations of precursors and organic co-reactants can be used to tailor the composition and resulting properties of the deposited resist film. As an example, the DtS can be adjusted by mixing different precursors. For example, using a first tin-containing precursor with a first alkyl group, a second tin-containing precursor with a second alkyl group (where the first and second alkyl groups are different), and acetone as the organic co-reactant, can produce a DtS of 51.2 mJ / cm at HP14, as seen in FIG. 3A. 2 Using the same first tin-containing precursor with acetone as the organic co-reactant (thereby omitting the second tin-containing precursor), the resist film (e.g., single alkyl film) had a DtS of 100.8 mJ / cm for HP14. 2 (See FIG. 3B.) Both films were subjected to a post-exposure bake.

[0161] Such modified precursors (including one or more organometallic precursors with organic co-reactants) can be used to incubate or bake to modify the properties of the resist film. In one example, the DtS can be adjusted (e.g., decreased or increased) by incubating the deposited film at elevated temperatures. In one non-limiting example, the DtS can be adjusted by using the same film under different PEB conditions (e.g., different PEB temperatures).

[0162] Such precursors and organic co-reactants can be further used in combination with one or more corresponding reactants. The corresponding reactants preferably have 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 corresponding reactants include oxygen-containing corresponding reactants, e.g., O 2 , O 3 , water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, di- or polyhydroxy alcohols, fluorinated di- or polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, and combinations thereof. In various embodiments, the corresponding reactant reacts with the organometallic precursor or modified precursor by forming oxygen bridges between adjacent metal atoms. Other potential corresponding reactants include hydrogen sulfide and hydrogen disulfide, which can bridge metal atoms through sulfur bridges, and bis(trimethylsilyl)tellurium, which can bridge metal atoms through tellurium bridges. In addition, hydrogen iodide may be utilized to incorporate iodine into the film.

[0163] The various atoms present in the organic co-reactant and / or the counter reactant can be provided in a gradient film. In some embodiments of the techniques discussed herein, a non-limiting strategy that can further improve the EUV sensitivity in PR films is to form films in which the film composition has a vertical gradient, resulting in EUV sensitivity with depth. A homogeneous PR with a high absorption coefficient would require a higher EUV dose to ensure that the bottom is adequately exposed, due to the reduced light intensity throughout the film's depth. 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 more uniformly distributing the absorption (and secondary electron effects) 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).

[0164] The strategy of engineering vertical compositional gradients in PR films is 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 organic co-reactants and / or counter-reactants containing highly absorbing elements, and combinations of the above.

[0165] Compositional gradients in EUV PR films can also provide additional benefits. For example, a high density of high 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 fraction 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.

[0166] Such gradient films can be formed using any of the organometallic precursors (e.g., tin or non-tin precursors), organic co-reactants, counter reactants, and / or modified precursors 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, and International Application No. PCT / US20 / 53856, filed October 1, 2020, published as WO 2021 / 067632, each entitled SUBSTRATE SURFACE MODIFICATION WITH HIGH EUV ABSORBERS FOR HIGH PERFORMANCE EUV PHOTORESISTS, and International Application No. PCT / US20 / 53856, filed June 24, 2020, published as WO 2020 / 264557 ... No. PCT / US20 / 70172, entitled "GRADIENT," the disclosure of which pertains at least to the composition, deposition, and patterning of directly photopatternable metal oxide films to form EUV resist masks, is incorporated herein by reference.

[0167] Additionally, 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 telluride can be RTaH, RTaD, or TeR. 2 -NR together with the precursor 2 In another example, a tellurium-containing precursor containing a trialkylsilyl ligand (e.g., bis(trimethylsilyl)tellurium) can be used in combination with an alkoxy or halo ligand (e.g., SbCl 3 Metal tellurides can be formed by using a first metal precursor comprising:

[0168] 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.

[0169] Further Precursors As described herein, the films, layers, and methods herein can be used with any useful precursor. In some cases, the organometallic precursor has the following formula (III): MX n (III) where M is a metal, X is halo, and n is 2-4 depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary metal halides include SnBr 4 , SnCl 4 , SnI 4 , and SbCl 3 Examples include:

[0170] Another non-limiting metal-containing precursor has formula (IV): MR n (IV) where M is a metal and each R is independently H, optionally substituted alkyl, amino (e.g., -NR 2 (wherein each R is independently alkyl)), optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR 3 ) 2 (wherein each R is independently alkyl)), or optionally substituted trialkylsilyl (e.g., -SiR 3 (each R is independently an 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 is C n H 2n+1 (n may be 1, 2, 3 or more). Exemplary organometallic agents include SnMe 4 , SnEt 4 , TeRn , RTeR, t-butyl tellurium hydride (Te(t-Bu)(H)), dimethyl tellurium (TeMe 2 ), di(t-butyl)tellurium (Te(t-Bu) 2 ), di(isopropyl)tellurium (Te(i-Pr) 2 ), bis(trimethylsilyl)tellurium (Te(SiMe 3 ) 2 ), bis(triethylsilyl)tellurium (Te(SiEt 3 ) 2 ), tris(bis(trimethylsilyl)amide)bismuth (Bi[N(SiMe 3 ) 2 ] 3 ), Sb(NMe 2 ) 3 etc.

[0171] Another non-limiting metal-containing precursor has the following formula (V): ML n (V) where 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 (R is alkyl as any described herein), halo, or other organic substituents, and n is 2-4, depending on the selection of M. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary ligands include dialkylamino (e.g., dimethylamino, methylethylamino, and diethylamino), alkoxy (e.g., t-butoxy, and isopropoxy), halo (e.g., F, Cl, Br, and I), or other organic substituents (e.g., acetylacetone or N 2 ,N 3 -di-tertbutyl-butane-2,3-diamino). Non-limiting capping agents include SnCl 4 , SnI 4 , Sn(NR2 ) 4 (each R is independently methyl or ethyl), or Sn(t-BuO) 4 In some embodiments, more than one type of ligand is present.

[0172] The metal-containing precursor has the following formula (VI): R n MX m (VI) where M is a metal and R is a C 2-10 The hydrocarbyl substituted capping agent may include a hydrocarbyl substituted capping agent having an alkyl or substituted alkyl, X being a suitable leaving group upon reaction with one of the exposed hydroxyl groups. In various embodiments, n=1-3, and m=4-n, 3-n, or 2-n, so long as m>0 (or m≧1). For example, R may be t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n-pentyl, n-hexyl, or a derivative thereof having a heteroatom substituent at the β position. Suitable heteroatoms include halogen (F, Cl, Br, or I), or oxygen (-OH or -OR). X may 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)(NMe 2 ) 3 ), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe 2 ) 3 ), t-butyltris(diethylamino)tin (Sn(t-Bu)(NEt 2 ) 3 ), di(t-butyl)di(dimethylamino)tin (Sn(t-Bu) 2 (NMe 2 ) 2), sec-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe 2 ) 3 ), n-pentyltris(dimethylamino)tin (Sn(n-pentyl)(NMe 2 ) 3 ), i-butyltris(dimethylamino)tin (Sn(i-Bu)(NMe 2 ) 3 ), i-propyltris(dimethylamino)tin (Sn(i-Pr)(NMe 2 ) 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 ) are mentioned.

[0173] In various embodiments, the metal-containing precursor comprises at least one alkyl group on each metal atom that can survive the gas phase reaction, and other ligands or ions coordinated to the metal atom can be displaced with corresponding reactants. Thus, another non-limiting metal-containing precursor is represented by formula (VII): M a R b L c (VII) where M is a metal, R is an optionally substituted alkyl, L is a ligand, ion, or other moiety reactive with a corresponding 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 2Each of may be H or alkyl as any described herein), alkoxy (e.g., -OR (R is alkyl as any described herein), or halo (e.g., F, Cl, Br, or I). Exemplary organometallic agents include SnMe 3 Cl, SnMe 2 Cl 2 , SnMeCl 3 , SnMe(NMe 2 ) 3 , SnMe 3 (NMe 2 ) etc.

[0174] In other embodiments, the non-limiting metal-containing precursor has formula (VIII): M a L c (VIII) where M is a metal and L is a ligand, ion, or other moiety that is reactive with a corresponding reactant, a≧1, and c≧1. In certain embodiments, c=n−1, and n is 2, 3, or 4. In some embodiments, M is Sn, Te, Bi, or Sb. The corresponding reactant preferably has the ability to displace the reactive moiety ligand or ion (e.g., L in the formulas herein) to link at least two metal atoms via a chemical bond.

[0175] In any embodiment herein, R is optionally substituted alkyl (e.g., C 1-10 In one embodiment, the alkyl can be one or more halo (e.g., halo-substituted C 1-10 alkyl and substituted with one, two, three, four or more halo, including, for example, F, Cl, Br, or I. Exemplary R substituents include C n H 2n+1 (preferably n≧3), and C n F x H (2n+1-x)(2n+1≦x≦1). In various embodiments, R has at least one β hydrogen or β fluorine. For example, R can 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.

[0176] In any embodiment herein, L is any moiety that is readily displaced by a corresponding reactant to generate an M-OH moiety, such as amino (e.g., -NR 1 R 2 (R 1 and R 2 Each of may be a moiety selected from the group consisting of H or alkyl as any described herein), alkoxy (e.g., -OR (R is alkyl as any described herein), carboxylate, halo (e.g., F, Cl, Br, or I), and mixtures thereof.

[0177] In certain embodiments, the metal precursor comprises tin. In some embodiments, the tin precursor is SnR or SnR 2 or SnR 4 or R 3 SnSnR 3 each R is independently selected from 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 2-12 Alkenyl, optionally substituted C 2-12 Alkynyl, optionally substituted C 3-8 Cycloalkyl, optionally substituted aryl, cyclopentadienyl, optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR 1 R 2 R 3 ) 2), optionally substituted alkanoyloxy (e.g., acetate), diketonate (e.g., -OC(R 1 )-Ak-(R 2 )CO-), or bidentate 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 1-6 Non-limiting examples of tin precursors include SnF 2 , SnH 4 , SnBr 4 , SnCl 4 , SnI 4 , tetramethyltin (SnMe 4 ), tetraethyltin (SnEt 4 ), trimethyltin chloride (SnMe 3 Cl), dimethyltin dichloride (SnMe 2 Cl 2 ), methyltin trichloride (SnMeCl 3 ), tetraallyltin, tetravinyltin, hexaphenylditin(IV)(Ph 3 Sn-SnPh 3 (Ph is phenyl), dibutyldiphenyltin (SnBu 2 Ph 2 ), trimethyl(phenyl)tin (SnMe 3 Ph), trimethyl(phenylethynyl)tin, tricyclohexyltin hydride, tributyltin hydride (SnBu 3 H), dibutyltin diacetate (SnBu 2 (CH 3 COO) 2 ), tin(II) acetylacetonate (Sn(acac) 2 ), SnBu 3 (OEt), SnBu 2 (OMe) 2 , SnBu 3(OMe), Sn(t-BuO) 4 , Sn(n-Bu)(t-BuO) 3 , tetrakis(dimethylamino)tin (Sn(NMe 2 ) 4 ), tetrakis(ethylmethylamino)tin (Sn(NMeEt) 4 ), tetrakis(diethylamino)tin(IV) (Sn(NEt 2 ) 4 ), (dimethylamino)trimethyltin(IV) (Sn(Me) 3 (NMe 2 ), Sn(i-Pr)(NMe 2 ) 3 , Sn(n-Bu)(NMe 2 ) 3 , Sn(s-Bu)(NMe 2 ) 3 , Sn(i-Bu)(NMe 2 ) 3 , Sn(t-Bu)(NMe 2 ) 3 , Sn(t-Bu) 2 (NMe 2 ) 2 , Sn(t-Bu)(NEt 2 ) 3 , Sn(tbba), Sn(II) (1,3-bis(1,1-dimethylethyl)-4,5-dimethyl-(4R,5R)-1,3,2-diazastannolidin-2-ylidene), or bis[bis(trimethylsilyl)amino]tin (Sn[N(SiMe 3 ) 2 ] 2 ) are mentioned.

[0178] Exemplary organometallic agents include SnMeCl 3 , (N 2 ,N 3 -di-t-butyl-butane-2,3-diamide)tin(II) (Sn(tbba)), bis(bis(trimethylsilyl)amido)tin(II), tetrakis(dimethylamino)tin(IV) (Sn(NMe 2 ) 4 ), t-butyltris(dimethylamino)tin (Sn(t-butyl)(NMe 2 )3 ), i-butyltris(dimethylamino)tin (Sn(i-Bu)(NMe 2 ) 3 ), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe 2 ) 3 ), sec-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe 2 ) 3 ), i-propyl(tris)dimethylaminotin (Sn(i-Pr)(NMe 2 ) 3 ), n-propyltris(diethylamino)tin (Sn(n-Pr)(NEt 2 ) 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.

[0179] Film composition A patterned radiation-sensitive film can be formed by using one or more modified precursors, optionally in the presence of one or more corresponding reactants. Furthermore, the modified precursors can be deposited (e.g., using any of the deposition processes described herein), exposed, incubated, and optionally further processed (e.g., baked, treated, annealed, plasma exposed, etc.) to provide a metal oxide layer (e.g., a layer comprising a network of metal oxide bonds, which may also include other non-metallic and non-oxygen groups).

[0180] The present disclosure encompasses a stack including a semiconductor substrate having an upper surface and a patterned radiation-sensitive film disposed on the upper surface of the semiconductor substrate. In some embodiments, the film includes a radiation-absorbing unit (e.g., a radiation-sensitive element) and a radiation-sensitive carbon-containing unit from an organic co-reactant (e.g., a radiation-responsive organic moiety such as any described herein). In certain embodiments, the radiation-sensitive carbon-containing unit is a bound ligand formed as a reaction product between the radiation-absorbing unit (e.g., in an organometallic precursor) and the organic co-reactant. Non-limiting examples of radiation-absorbing units include metals or metalloids (e.g., tin (Sn), tellurium (Te), hafnium (Hf), and zirconium (Zr), or combinations thereof). In other embodiments, the radiation-sensitive carbon-containing unit is selected from the group of an alkenylene moiety, an alkynylene moiety, a carbonyl moiety, and a dicarbonyl moiety, or combinations thereof. The film can be exposed to light (to provide an exposed film) and then incubated (to provide an incubated film).

[0181] 4A illustrates an exemplary stack including a substrate 401 (e.g., a semiconductor substrate) having a top surface and a film 402 disposed on the top surface of the substrate 401. The film may include any useful patterning radiation sensitive material (e.g., an EUV sensitive material such as any described herein that may be useful as a PR). In some embodiments, the patterning radiation sensitive film includes a modified precursor or a deposit thereof. The deposit may include a metal-organic material, such as an organometallic oxide (e.g., an RM(MO) n (M is a metal and R is an organic moiety having one or more carbon atoms, such as in alkyl, alkylamino, or alkoxy). 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., photoresist layer), or device.

[0182] The EUV-sensitive film may include radiation-absorbing units and radiation-sensitive carbon-containing units. In some embodiments, the radiation-absorbing units include or are EUV-absorbing units. Non-limiting examples of these include, for example, 1×10 7 cm 2 and metals with large EUV absorption cross sections, such as equal to or greater than 1000000000 / mol. In other embodiments, the radiation absorbing unit includes or is M (e.g., M can be Sn, Te, Bi, Sb, Hf, or Zr, or a combination thereof). In some embodiments, the radiation sensitive carbon-containing unit is an EUV sensitive carbon-containing unit. In certain embodiments, the EUV sensitive carbon-containing unit includes an organic co-reactant or a reaction product thereof. Non-limiting examples of EUV sensitive carbon-containing units include, for example, any of the organic moieties described herein (e.g., alkenylene moieties, alkynylene moieties, carbonyl moieties, dicarbonyl moieties, or combinations thereof).

[0183] In some embodiments, the EUV-sensitive film may be characterized by an increase or decrease in carbon content, such as an increase in metal-carbon or oxygen-carbon bonds, or an increase in various organic moieties, such as alkenylene, alkylene, carbonyl, or dicarbonyl moieties (e.g., substituted alkylene groups having two carbonyl moieties). The presence or use of an organic co-reactant in the film may be detected in any useful manner. Non-limiting methods include, for example, using Fourier transform infrared (FTIR) spectroscopy, solid-state nuclear magnetic resonance (NMR) spectroscopy, and / or ultraviolet-visible (UV-Vis) spectroscopy to detect functional groups present in the organic co-reactant. The increase or decrease in organic carbon content can optionally increase the porosity of the film compared to a film formed without the organic co-reactant. Non-limiting methods of measuring porosity include, for example, volumetric gas adsorption.

[0184] In some embodiments, the EUV sensitive film comprises a vertical gradient characterized by a change in EUV absorbance. In certain embodiments, the vertical gradient comprises an increase in EUV absorbance, where the bottom of the film adjacent to the substrate has a higher EUV absorbance than the top of the film. In other embodiments, the vertical gradient comprises a decrease in carbon content, where the bottom of the film adjacent to the substrate has a lower carbon content than the top of the film. In yet other embodiments, the vertical gradient comprises an increase in carbon content, where the bottom of the film adjacent to the substrate has a higher carbon content than the top of the film.

[0185] The film can have a vertical gradient characterized by a vertical change in EUV absorbance (e.g., non-limiting methods and properties of gradient films are described herein). 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 a decrease in carbon content along the same depth through the film layer. In other examples, an increase in EUV absorbance along the depth can correspond to an increase in tellurium, antimony, or iodine content along the same depth through the film layer.

[0186] FIG. 4B illustrates an exemplary stack including a substrate 411 (e.g., a semiconductor substrate) having a top surface and a film 412 disposed on the top surface of the substrate 411, the film 412 having a vertical gradient characterized by a change in EUV absorbance and / or carbon content. For example, the gradient film 412 may include a first concentration of carbon content at a top 412a of the film and a second concentration of carbon content at a bottom 412b of the film, where the first and second concentration values ​​are different. In one example, the first concentration is greater than the second concentration. In another example, the first concentration is less than the second concentration. Non-limiting gradients include linear gradients, exponential gradients, sigmoidal gradients, and the like. In certain embodiments, a gradient density film of EUV reactive organic moieties can result in more uniform 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 LWR and / or LER).

[0187] In some embodiments, the stack includes a photoresist layer having radiation absorbing units and radiation sensitive carbon-containing units, hi other embodiments, the stack includes a capping layer (which may, for example, include radiation absorbing units and radiation sensitive carbon-containing units).

[0188] The patterning radiation sensitive film (e.g., EUV sensitive film) can be used as a capping layer, which is then disposed on any useful layer or structure. As seen in FIG. 4C, the stack may include a substrate 421 (e.g., a semiconductor substrate) having an upper surface, which further includes a photoresist layer 422. The EUV sensitive film 423 is a capping layer disposed on the upper surface of the photoresist layer 422. Such a capping layer may function to reduce off-gassing that may occur during EUV exposure of the underlying photoresist layer. This capping layer may also provide a barrier against chemical species generated during the EUV patterning process. In particular, if the photoresist layer is formed from a metal-containing precursor (e.g., an organometallic agent, a metal halide, and any described herein), then the capping layer may capture metals or chemical species generated during EUV exposure, thus minimizing contamination of the lithography apparatus. The capping layer can be of any useful thickness (e.g., any of the thicknesses described herein, including about 0.1 nm to about 5 nm, e.g., about 0.1 nm to 0.5 nm, 0.1 nm to 1 nm, 0.1 nm to 3 nm, 0.3 nm to 0.5 nm, 0.3 nm to 1 nm, 0.3 nm to 3 nm, 0.3 nm to 5 nm, 0.5 nm to 1 nm, 0.5 nm to 3 nm, 0.5 nm to 5 nm, 0.8 nm to 1 nm, 0.8 nm to 3 nm, 0.8 nm to 5 nm, 1 nm to 3 nm, 1 nm to 5 nm, or 3 nm to 5 nm).

[0189] The capping layer can be provided in any useful manner. In one example, the method includes providing a substrate including a photoresist layer, then depositing a modification precursor (e.g., formed in situ by providing an organometallic precursor in the presence of an organic co-reactant) on the surface of the photoresist layer. In this manner, the capping layer is formed from the modification precursor and serves to protect the photoresist layer, which may then also include an EUV-sensitive material. The EUV-sensitive materials of the capping layer and the photoresist layer can have different metal / carbon ratios, and the capping layer 423 can have an increased carbon content compared to the photoresist layer 422. The capping layer is present during patterning and, in some cases, can reduce the release of volatile chemical and metal species from the photoresist layer during EUV exposure.

[0190] In certain embodiments, different metal to carbon ratios can be achieved by using the same organometallic precursor and the same organic co-reactant in both the capping layer and the photoresist layer, but the ratio of organometallic precursor to organic co-reactant can be adjusted during deposition to result in different metal / carbon ratios. In other embodiments, different metal / carbon ratios can be achieved by using the same organometallic precursor but different organic co-reactants in the two layers. For example, the capping layer may include the use of a co-reactant with a bulkier organic substituent (e.g., ethyl, propyl, or butyl) than the organic substituent (e.g., methyl) of the co-reactant in the photoresist layer.

[0191] The photoresist layer 422 can be provided in any useful manner. In one example, the photoresist layer is provided by depositing an organometallic precursor (e.g., an organometallic agent, a metal halide, or any of the above), optionally in the presence of a corresponding reactant. In another example, the photoresist layer is provided by depositing an organometallic precursor in the presence of an organic co-reactant. After the photoresist layer is created, a capping layer can be provided.

[0192] Lithography Process EUV lithography utilizes an EUV resist, which may be a polymer-based chemically amplified resist produced by a liquid-based spin-on technique, or a metal oxide-based resist produced by a dry vapor deposition technique. Such an EUV resist may include any of the EUV-sensitive films or materials described herein. The lithography method may 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.

[0193] 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 encompass 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 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.

[0194] Directly photopatternable EUV resists may be composed of or include metals and / or metal oxides mixed within an organic component. The metals / metal oxides may enhance EUV photon adsorption, generate secondary electrons, and / or exhibit increased etch selectivity relative to the underlying film stack and device layers. These resists can be developed using wet (solvent) approaches, dry approaches, or a combination thereof.

[0195] Wet approaches may include using the wafer on a track, exposing it to a developing solvent, drying, and baking. For wet development, such processes may be optimized to eliminate substrate delamination and interface defects. Dry approaches may include the use of steam to remove the desired PR regions. For dry development, such processes may be optimized to increase the etch selectivity between unexposed and EUV-exposed resist materials, reduce PR corner rounding that may result from long exposure under etching gases, and reduce line CD variations in the subsequent transfer etch step. Additional processes used during lithography are described in detail below.

[0196] Deposition processes, including dry deposition As mentioned above, the present disclosure provides a method for producing an imaging layer on a semiconductor substrate, which can be patterned using EUV or other next generation lithography techniques. Methods include a method 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., a metal halide, a capping agent, or an organometallic agent described herein). In other embodiments, a spin-on formulation 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.

[0197] 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.

[0198] 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 them to crosslink 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 resulting in a higher density MLM-bonded organometallic material (where L is a ligand). In yet other embodiments, EUV exposure results in loss of ligands, resulting in an M-OH material that can be removed by a positive tone developer.

[0199] EUV patterning creates regions of the film with altered physical or chemical properties compared to non-exposed regions. These properties can be exploited in subsequent processing, such as dissolving either the non-exposed or exposed regions, or selectively depositing material in either the exposed or non-exposed regions. In some embodiments, under the conditions under which such subsequent processing is carried out, the non-exposed film has a hydrophobic surface and the exposed film has a hydrophilic surface (it being recognized that the hydrophilic properties of the exposed and non-exposed regions are relative to one another). 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 and / or dry processing, as further described herein.

[0200] The thickness of the EUV patternable film formed on the surface of the substrate can vary according to the surface characteristics, the materials used, and the processing conditions. In various embodiments, the film thickness can 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 can 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 adequately exposed. In some embodiments, the film thickness is 10 to 20 nm. In some embodiments, the deposited film conforms closely to surface features, which can provide advantages in forming a mask over a substrate, such as a substrate having underlying features, without "filling" or otherwise planarizing such features.

[0201] 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 of the EUV-sensitive materials described herein, such as metal-containing precursors (e.g., metal halides, capping agents, or organometallic agents) in combination with organic co-reactants. 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.

[0202] Optionally, the metal oxide layer may include a hydroxyl-terminated metal oxide layer, which may be deposited by using a capping agent (e.g., any described herein) with an oxygen-containing corresponding reactant. Such a hydroxyl-terminated metal oxide layer may 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.

[0203] 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, and the like, or combinations thereof, such as ALD with CVD components, such as a metal-containing precursor, an organic co-reactant, and a discontinuous ALD-like process in which the corresponding reactants are separated either in time or space.

[0204] Further description of precursors as EUV photoresist films applicable to the present disclosure, and methods for depositing the precursors, 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 may include optional materials in addition to the organometallic precursors, organic co-reactants, and counter reactants to modify the chemical or physical properties of the film, such as to modify the film's sensitivity to EUV or to enhance 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, mild remote H 2 By introducing a plasma, for example, some Sn-L bonds can be replaced by Sn-H, which can increase the reactivity of the resist under EUV.

[0205] In general, the method may include mixing a vapor flow of an organometallic precursor (e.g., a metal-containing precursor such as an organometallic agent) with a vapor flow of an organic co-reactant and an optional corresponding 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 may be mixed with the organic co-reactant and an optional corresponding reactant to form a polymerized organometallic material. As will be appreciated by one of ordinary skill in the art, the mixing and deposition aspects of the process may be simultaneous in a substantially continuous process.

[0206] In an exemplary sequential CVD process, gas flows of two or more of the sources of organometallic precursor, organic co-reactant, and optional corresponding reactant are introduced in separate inlet paths into a deposition chamber of a CVD apparatus where the gas flows mix and react in the gas phase to form a coagulated polymeric material or film on a substrate (e.g., via metal-oxygen-metal bond formation). The gas flows can be introduced, for example, using separate inlets or a dual plenum showerhead. The apparatus is configured such that the flows of organometallic precursor, organic co-reactant, and optional corresponding reactant are mixed in the chamber, thereby allowing the organometallic precursor, organic co-reactant, and optional corresponding reactant to react and form a polymerized organometallic material or film (e.g., a metal oxide coating or coagulated polymeric material via metal-oxygen-metal bond formation, etc.).

[0207] To deposit metal oxides, the CVD process is generally 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 streams. For example, the substrate temperature can be from 0 to 250° C., or from ambient temperature (e.g., 23° C.) to 150° C.

[0208] To deposit the coagulated polymeric material, the CVD process is generally carried out at reduced pressure, such as 10 mTorr to 10 Torr. In some embodiments, the process is carried out at 0.5 to 2 Torr. The temperature of the substrate is preferably at or below the temperature of the reactant flow. 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 the metal atoms are crosslinked by organic co-reactants and / or counter-reactants, and are then condensed or otherwise deposited onto the substrate. In various embodiments, steric hindrance of the bulky alkyl groups (e.g., provided by organic co-reactants) further prevents the formation of densely packed networks, producing a low density film with increased porosity.

[0209] A potential advantage of using dry deposition methods is that the composition of the film can be easily tuned as it grows. In a CVD process, this can be achieved by altering the relative flow rates of the organometallic precursor and the organic co-reactant 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.

[0210] 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, an organometallic precursor, an organic co-reactant, and an optional counter reactant are introduced at separate times, which represent ALD cycles. The precursor and the organic co-reactant 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 0.1-10 Torr. In some embodiments, the process is performed at 1-2 Torr. The substrate temperature can be 0-250° C., or ambient (e.g., 23° C.) to 150° C. The process can be a thermal process, or preferably, a plasma-assisted deposition.

[0211] Any of the deposition methods herein can be modified to allow for the use of two or more different organometallic precursors. In one embodiment, the precursors may contain the same metal but different ligands. In another embodiment, the precursors may 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).

[0212] Also, any of the deposition methods herein can be modified to allow for the use of two or more different organic co-reactants. In one embodiment, the organic co-reactants can provide different binding ligands to the metal center. In one non-limiting example, alternating flows of various organic co-reactants can provide layers with different carbon contents, such as in gradient films.

[0213] 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 organometallic precursors and / or organic co-reactants can be used in 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., a different density of metal-ligand bonds, a different metal / carbon ratio, or different binding ligands, such as provided by adjusting or modifying the organic co-reactant).

[0214] The processes herein can be used to achieve surface modification. In some iterations, vapors of organometallic precursors 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 from about 50° C. to 250° C. In some cases, pulses of organic co-reactant can be used, separated by pumping and / or purging steps. For example, the organic co-reactant can be pulsed between pulses of precursor to provide ALD or ALD-like growth. In other cases, both the precursor and organic co-reactant may be flowed simultaneously. Examples of elements useful for surface modification include I, F, Sn, Bi, Sb, Te, and oxides or alloys of these compounds.

[0215] The processes herein can be used to deposit thin metal oxides or metals by ALD or CVD. Examples include SnO x , BiO x Following deposition, the films are then thermally treated with M, Te, and Te as described elsewhere herein. a R b L c The ligands can be better removed using the corresponding reactants, and multiple cycles can be repeated to ensure complete saturation of the substrate surface. The surface is then ready for deposition of an EUV-sensitive film. One possible method is to use SnO xThe possible chemicals are tetrakis(dimethylamino)tin and water or O 2 SnO by circulating the corresponding reactant such as plasma 2 After growth, a capping agent can be used, for example, vapor of isopropyltris(dimethylamino)tin can be flowed over the surface.

[0216] 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.

[0217] 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 having features formed thereon that have irregular surface topography ("underlying topographical features").

[0218] Such underlying topographical features may include areas from which material has been removed (e.g., by etching) or added (e.g., by deposition) during processing prior to performing the methods of the technique. Such pre-processing may include other processing methods in the methods of the technique or in an iterative process whereby two or more layers of features are formed on the substrate. In some embodiments, the film is configured to conform to the underlying features without "filling" or otherwise planarizing such features, thereby allowing such films to be deposited on a wide variety of material surfaces.

[0219] 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.

[0220] In some embodiments, the substrate is a hard mask used in the lithographic etching of the underlying semiconductor material. Hard masks can be made of amorphous carbon (aC), tin oxide (e.g., SnO x ), silicon oxide (e.g., SiO 2 ), silicon oxynitrides (e.g., SiO x N y ), silicon oxycarbide (e.g., SiO x C y ), silicon nitride (e.g., Si 3 N 4 ), titanium oxide (e.g., TiO 2 ), titanium nitride (e.g., TiN), tungsten (e.g., W), doped carbon (e.g., W-doped C), tungsten oxide (e.g., WO x ), hafnium oxide (e.g., HfO 2 ), zirconium oxide (e.g., ZrO 2 ), and aluminum oxide (e.g., Al 2 O 3 ) For example, the substrate is preferably SnO 2SnO x In various embodiments, the layer can be 1 to 100 nm thick, or 2 to 10 nm thick.

[0221] 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 can be to 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 or dry deposition 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 may 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.

[0222] In some embodiments, a surface activation operation can be used to activate the 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-based or hydrocarbon-based surfaces, various treatments (e.g., water, hydrogen / oxygen, CO 2Plasma, or ozone treatments) can be used to create carboxylic acid and / or hydroxyl groups. Such approaches may prove important in improving adhesion of resist features to the substrate, which in some cases may peel or lift off in solvents during handling or development.

[0223] Adhesion can also be enhanced by inducing roughness in the surface to increase the surface area available for interaction and directly improve mechanical adhesion. For example, a sputtering process using Ar or other non-reactive ion bombardment can first be used to generate a rough surface. The surface can then be terminated with the desired surface functional groups (e.g., hydroxyl and / or carboxylic acid groups) as described above. On carbon, CO 2 , O 2 , or H 2 O (or H 2 and O 2 A combination approach can be used in which a chemically reactive oxygen-containing plasma such as a mixture of oxygen and oxygen-containing fluorine (OxO) can be used to etch away thin layers of films with localized inhomogeneities while simultaneously terminating them with -OH, -OOH, or -COOH groups. This approach can be performed with or without bias. In conjunction with the surface modification strategies mentioned above, this approach can serve the dual purpose of roughening and chemically activating the substrate surface, either for direct adhesion to inorganic metal oxide-based resists or as an intermediate surface modification for further functionalization.

[0224] In various embodiments, the surface (e.g., of a substrate and / or membrane) includes exposed hydroxyl groups on its surface. In general, the surface can be any surface that includes or has been treated to generate exposed hydroxyl surfaces. 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 membrane 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.

[0225] EUV exposure process EUV exposure of the film can provide EUV-exposed regions with activated reactive centers comprising a metal atom (M) that are generated by EUV-mediated cleavage events. 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 crosslinked organic moieties by photopolymerizing ligands within the film, or EUV exposure releases gaseous by-products resulting from photolysis of bonds within the ligands.

[0226] 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 form a pattern by providing an EUV exposed region and an EUV non-exposed region.

[0227] The techniques may include patterning using EUV, as well as DUV or e-beam. In such patterning, radiation is focused on one or more regions of the imaging layer. Exposure may be performed such that the imaging layer film includes one or more regions that are not exposed to radiation. The resulting imaging layer may include multiple exposed and unexposed regions, 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.

[0228] In some EUV lithography techniques, an organic hardmask (e.g., a PECVD amorphous hydrogenated carbon ashable hardmask) is patterned using a photoresist process. During photoresist exposure, EUV radiation is absorbed by the resist and the underlying substrate, generating high-energy photoelectrons (e.g., about 100 eV) 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, thereby increasing the EUV dose sensitivity of the resist. 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 line width variations in the patterned resist. These defects are replicated in the material being patterned during the subsequent pattern-transfer etch.

[0229] 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.

[0230] 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 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 Lam2300® Kiyo®).

[0231] Following deposition, the EUV-patternable thin film is patterned by exposure to a beam of EUV light, which can be performed under a relatively high vacuum. For EUV exposure, the metal-containing film can then 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 that it is unreactive prior to exposure. Integration with the lithography tool is achieved by using a H 2 O, O 2 This is facilitated by the fact that EUVL also requires significantly reduced pressures, given the strong optical absorption of incident photons by ambient gases such as SiO 2 , etc. In another embodiment, photosensitive metal film deposition and EUV exposure can occur in the same chamber.

[0232] Development processes include dry development and wet development The EUV exposed or unexposed regions, as well as the capping layer, can be removed by any useful development process. In an 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 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.

[0233] Dry development processes may involve the use of various compounds in gaseous or vapor form. For example, such processes may involve the use of gaseous water (H 2 O), oxygen (O 2 ), gaseous acids, gaseous halides, or combinations thereof. Non-limiting gaseous acids include hydrochloric acid (HCl), hydrobromic acid (HBr), hydrofluoric acid (HF), sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ), trifluoroacetic acid, trifluoroacetic anhydride, etc. Non-limiting examples of gaseous halides include tetrafluoromethane (CF 4 ), boron trichloride (BCl 3 ), HCl, HBr, and combinations thereof. Combinations of gaseous water and gaseous acid, or O 2 Combinations such as a combination of a sulphuric acid and a gaseous acid can be used.

[0234] Dry development processes may also include the use of halides, such as HCl- or HBr-based processes. Although this disclosure is not limited to any particular theory or mechanism of operation, an approach may involve the use of a dry-deposited EUV photoresist film and clean chemistry (e.g., HCl, HBr, and BCl 3 ) to form volatile products using vapor or plasma. Dry-deposited EUV photoresist films can be removed at etch rates 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. The films can be removed by vapors at various temperatures (e.g., HCl or HBr at temperatures above -10°C, or BCl at temperatures above 80°C, for example). 3 ), but it is also possible to use a plasma to further promote or enhance reactivity.

[0235] 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 carried out at a pressure of greater than 0.5 mTorr (e.g., 1 to 100 mTorr, etc.) and a power level of less than 1000 W (e.g., less than 500 W). The temperature can be 30 to 300° C. (e.g., 30 to 120° C.) with a flow rate of 100 to 1000 standard cubic centimeters per minute (sccm), e.g., about 500 sccm, for 1 to 3000 seconds (e.g., 10 seconds to 600 seconds).

[0236] If the halide reactant stream is hydrogen gas and a halide gas, remote plasma / UV radiation can be used to generate H 2 and Cl 2 and / or Br 2Radicals are generated from the hydrogen and halide radicals and flowed into a reaction chamber to contact the patterned EUV photoresist on the substrate layer of the wafer. Suitable plasma power can range from 100 to 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.

[0237] 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 may include a vacuum line, a dry development hydrogen halide chemical gas (e.g., HBr, HCl) line, and a heater for temperature control. In some embodiments, the 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.

[0238] Process conditions for dry development can be reactant flow rates of 100-500 sccm (e.g., 500 sccm HBr or HCl), temperatures of -10 to 120°C (e.g., -10°C), pressures of 1 to 500 mTorr (e.g., 300 mTorr) for times of about 10 seconds to 1 minute without plasma, depending on the photoresist film and capping layer and their compositions and properties.

[0239] In various embodiments, the disclosed method combines 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 provide additional CD control and / or scum removal.

[0240] In various embodiments, the EUV photoresist containing some amount of metal, metal oxide, and organic components has the formula R x Z y The dry development can be carried out by heat, plasma (which may include, for example, light-activated plasma such as lamp heating or UV lamp heating), or a combination of heat and plasma methods while flowing a dry development gas containing a compound of the formula: 4 and y>0. Dry development is R x Z y The photoresist film can be photodeveloped in a positive tone, where the species selectively removes the exposed material, leaving the unexposed counterpart as a mask. In some embodiments, the exposed portions of the organotin oxide-based photoresist film are removed by dry development in accordance with the present disclosure. Positive tone dry development can be achieved by applying a flow containing hydrogen halides or hydrogen and halides (including HCl and / or HBr) without applying a plasma, or H with a remote plasma or UV radiation generated from a plasma to generate radicals. 2 and Cl 2 and / or Br 2 This can be achieved by selective dry development (removal) of the EUV exposed areas exposed to a flow of

[0241] Wet development techniques can also be used. In certain embodiments, such wet development techniques are used to remove EUV exposed areas and provide a positive photoresist or a negative resist. In some embodiments, wet development is performed using a neutral developer (e.g., a pH neutral developer such as water) or a peroxide-containing developer (e.g., hydrogen peroxide, H 2 O 2 Exemplary, non-limiting wet development processes include those that include a base, such as ammonium, in an alkaline developer (e.g., an aqueous alkaline developer), such as ammonium hydroxide (NH 4 OH), ammonium-based ionic liquids such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), or other quaternary alkylammonium hydroxides, organic amines such as mono-, di-, and tri-organic amines (e.g., diethylamine, diethylamine, ethylenediamine, triethylenetetramine), or alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, or diethyleneglycolamine. In other embodiments, the alkaline developer may include the use of nitrogen-containing bases, such as those of the formula R N1 NH 2 , 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., 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.

[0242] Other development methodologies may 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 an acidic developer.

[0243] In certain embodiments, the positive developer is an aqueous alkaline developer (e.g., NH 4 OH, TMAH, TEAH, TPAH, or TBAH). In other embodiments, the negative tone developer is an aqueous acid developer, an acid 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).

[0244] Any of the developers herein may contain one or more surfactants. The surfactant may contain a positive, negative, or neutral charge 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.

[0245] 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.

[0246] The development process may 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. In one embodiment, the process includes the use of gaseous water, oxygen (O 2 ), gaseous acids, gaseous halides, or combinations thereof, as well as wet development processes having liquid water, aqueous solutions, or organic solvents (e.g., ketones such as any of those described herein).

[0247] Post-application process The methods herein may include any useful post-application processes, as described below.

[0248] 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 wafer surface. The 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.

[0249] Suitable process conditions for dry bevel edge and backside cleaning include reactant flow rates of 100-500 sccm (e.g., 500 sccm HCl, HBr, or H) for a time of about 10-20 seconds, depending on the photoresist film and composition and properties. 2 and Cl 2 or Br 2 , BCl 3 or H 2 ), a temperature of -10 to 120°C (e.g., 20°C), a pressure of 20 to 500 mTorr (e.g., 300 mTorr), and a plasma power of 0 to 500 W at a high frequency (e.g., 13.56 MHz). These conditions are suitable for some processing reactors, e.g., the Kiyo etch tool available from Lam Research, Inc. of 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.

[0250] The photolithography process may involve one or more bake steps to promote the chemical reactions necessary to create the chemical contrast between exposed and unexposed areas of the photoresist. For high volume manufacturing (HVM), such bake steps are performed in ambient air or possibly N 2 This may be performed on a track where the wafer is baked on a hot plate at a preset temperature under 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, may help to further reduce dose requirements and / or improve pattern fidelity.

[0251] 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 after exposure (e.g., post-exposure bake (PEB)) and / or after development (e.g., post-development 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.

[0252] For post-treatment (e.g., PAB), the temperature, gas atmosphere (e.g., air, H 2 O, CO 2 , C.O., O 2 , O 3 , C.H. 4 , C.H. 3 OH, N 2 , H 2 , N.H. 3 , N 2 Thermal processes under vacuum and moisture control (O, NO, Ar, He, or mixtures thereof) 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.

[0253] For post-exposure treatment (e.g., incubation or PEB), adjust the temperature, gas atmosphere (e.g., air, H 2 O, CO 2 , C.O., O 2 , O 3 , C.H. 4 , C.H. 3 OH, N 2 , H 2, N.H. 3 , N 2 The composition of both the unexposed and exposed photoresist can be changed using a thermal process under vacuum and controlled with oxygen (O, NO, Ar, He, or mixtures thereof) and moisture. This change can increase the difference in composition / material properties between the unexposed and exposed photoresist and the difference in the etch rate of the dry development etch gas between the unexposed and exposed photoresist. Thereby, a higher etch selectivity can be achieved. The improved selectivity can result in a squarer PR profile with improved surface roughness and / or less photoresist residue / scum. In certain embodiments, the PEB can be performed in air as well as in the presence of moisture and CO. 2 The method can be carried out in the optional presence of

[0254] For post-development treatment (e.g., post-development bake or PDB), the temperature, gas atmosphere (e.g., air, H 2 O, CO 2 , C.O., O 2 , O 3 , C.H. 4 , C.H. 3 OH, N 2 , H 2 , N.H. 3 , N 2 The composition of the unexposed photoresist can be changed using plasma (e.g., O, NO, Ar, He, or mixtures thereof) or under vacuum (e.g., using UV) and thermal processes to control moisture. In certain embodiments, the conditions can also be plasma (e.g., O 2 , O 3 , 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.

[0255] In these cases, in alternative implementations, the thermal process can be replaced with a remote plasma process, increasing the reactive species and lowering the energy barrier to the reaction, thus increasing productivity. Remote plasma can generate more reactive radicals, thus lowering the reaction temperature / time for processing, leading to increased productivity.

[0256] Thus, one or more processes can be applied to modify the photoresist itself, increasing the selectivity of 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. By adjusting process conditions, including temperature, gas flow, moisture, pressure, and / or RF power, the difference between the resulting material properties of the unexposed and exposed materials can be tailored. 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.

[0257] During wet development, the degree and number of temperature bakes can be optimized to obtain the desired development selectivity. For example, wet development can depend on the solubility of the materials, so that 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, thereby rendering both insoluble in the wet development solvent, and thus the film can no longer be reliably wet developed. For dry-developed resist films, where the difference in etch rate between exposed and unexposed regions of the PR (i.e., selectivity) 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 for PAB, e.g., 90-190°C, 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.

[0258] 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.

[0259] 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 a semiconductor processing operation, thermal treatments as described herein can be used to lower the required EUV dose. Alternatively, if a higher selectivity is required and a higher dose can be tolerated, it is possible to obtain a much higher selectivity (up to 100x exposed vs. unexposed).

[0260] Still 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 include, for example, a scatterometry module, an ellipsometry module, a downstream mass spectrometry module, and / or a plasma enhanced downstream optical emission spectroscopy module.

[0261] 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 an organometallic precursor in the presence of an organic co-reactant, a patterning module comprising an EUV photolithography tool having a radiation source at a wavelength less than 30 nm, and a developing module comprising a chamber for developing the film.

[0262] 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 depositing a film or a capping layer. Such inclusion may include depositing the modified precursor as a film on the top surface of a substrate or a 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.

[0263] 5 shows a schematic diagram of one embodiment of a process station 500 having a process chamber body 502 for maintaining a low pressure environment suitable for carrying out the described dry strip and development embodiments. Multiple process stations 500 may be included in a common low pressure process tool environment. For example, FIG. 6 shows one embodiment of a multi-station processing tool 600, 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 500 (including those discussed in detail below) may be programmatically adjusted by one or more computer controllers 550.

[0264] The process stations may be configured as modules within a cluster tool. Figure 8 illustrates a semiconductor process cluster tool architecture with a vacuum integrated deposition and patterning module suitable for implementing the embodiments described herein. Such a cluster process tool architecture may include resist deposition, resist exposure (EUV scanner), resist dry development, and etching modules as described herein with reference to Figures 5 and 7.

[0265] In some embodiments, certain processing functions can be performed sequentially in the same module, e.g., dry develop and etch. 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 develop / etch 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.

[0266] Returning to FIG. 5, the process station 500 is in fluid communication with a reactant delivery system 501a for delivering process gases to a distribution showerhead 506 via connection 505. The reactant delivery system 501a optionally includes a mixing vessel 504 for blending and / or adjusting the process gases delivered to the showerhead 506. One or more mixing vessel inlet valves 520 can control the introduction of process gases to the mixing vessel 504. If plasma exposure is used, the plasma may also be delivered to the showerhead 506 or may be generated at the process station 500. The process gases may include any described herein, such as, for example, an organic co-reactant, an organometallic precursor, or a corresponding reactant.

[0267] 5 includes an optional vaporization point 503 for vaporizing a liquid reactant provided to the mixing vessel 504. The liquid reactant may include an organic co-reactant, an organometallic precursor, or a counter reactant. In some embodiments, a liquid flow controller (LFC) may be provided upstream of the vaporization point 503 to control the mass flow rate of the liquid that is vaporized and delivered to the process station 500. 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.

[0268] 5, the substrate 512 is shown positioned below the showerhead 506 and resting on a pedestal 508. The showerhead 506 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to the substrate 512.

[0269] In some embodiments, the pedestal 508 can be raised or lowered to expose the substrate 512 to the space between the substrate 512 and the showerhead 506. It will be appreciated that in some embodiments, the height of the pedestal can be programmatically adjusted by a suitable computer controller 550.

[0270] In some embodiments, the pedestal 508 can be temperature controlled via a heater 510. In some embodiments, the pedestal 508 can be heated to 300° C. for 10 minutes at 3 ... 3 During non-plasma thermal exposure to dry developing chemistries such as , the substrate may be heated to a temperature of from above 0°C up to 300°C or more, such as from 50 to 120°C, for example from about 65 to 80°C.

[0271] Additionally, in some embodiments, pressure control for the process station 500 may be provided by a butterfly valve 518. As shown in the embodiment of Figure 5, the butterfly valve 518 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control for the process station 500 may also be adjusted by varying the flow rate of one or more gases introduced to the process station 500.

[0272] In some embodiments, the position of the showerhead 506 can be adjusted relative to the pedestal 508 to change the volume between the substrate 512 and the showerhead 506. Further, it will be understood that the vertical position of the pedestal 508 and / or the showerhead 506 may be changed by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 508 may include a rotation axis for rotating the orientation of the substrate 512. It will be understood that in some embodiments, one or more of these exemplary adjustments may be implemented programmatically by one or more suitable computer controllers 550.

[0273] Where plasma may be used, for example in a mild plasma-based dry development embodiment and / or an etching operation performed in the same chamber, the showerhead 506 and pedestal 508 are in electrical communication with a radio frequency (RF) power source 514 and matching network 516 to power the plasma 507. 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 514 and matching network 516 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.

[0274] In some embodiments, instructions for the controller 550 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 step. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe step. For example, a recipe step may include instructions for setting a flow rate of a dry development chemical reactant gas, such as HBr or HCl, and a time delay instruction for the recipe step. In some embodiments, the controller 550 may include any of the features described below with respect to the system controller 650 of FIG. 6.

[0275] As mentioned above, one or more process stations may be included in a multi-station processing tool. FIG. 6 shows a schematic diagram of an embodiment of a multi-station processing tool 600 with an inbound load lock 602 and an outbound load lock 604, either or both of which may include a remote plasma source. A robot 606 is configured to move a wafer from a cassette loaded via a pod 608 at atmospheric pressure to the inbound load lock 602 via an atmospheric port 610. The wafer is placed by the robot 606 on a pedestal 612 of the inbound load lock 602, the atmospheric port 610 is closed, and the load lock is pumped down. If the inbound load lock 602 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 614. Additionally, the wafer may also be heated in the inbound load lock 602 as well, for example to remove moisture and adsorbed gases. A chamber transfer port 616 to the processing chamber 614 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 shown in Figure 6 includes a load lock, it will be understood that in some embodiments direct entry of the wafer into the process stations may be provided.

[0276] The illustrated processing chamber 614 includes four process stations, numbered 1 through 4 in the embodiment shown in FIG. 6. Each station has a heated pedestal (shown at 618 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 614 may include one or more corresponding pairs of dry development and etch process stations. While the illustrated processing chamber 614 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, the processing chamber may have five or more stations, while in other embodiments, the processing chamber may have three or fewer stations.

[0277] FIG. 6 illustrates one embodiment of a wafer handling system 690 for transporting wafers within the processing chamber 614. In some embodiments, the wafer handling system 690 can transport 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. 6 also illustrates one embodiment of a system controller 650 used to control the process conditions and hardware states of the process tool 600. The system controller 650 may include one or more memory devices 656, one or more mass storage devices 654, and one or more processors 652. The processor 652 may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0278] In some embodiments, the system controller 650 controls all of the activities of the process tool 600. The system controller 650 executes system control software 658, which is stored in the mass storage device 654, loaded into the memory device 656, and executed by the processor 652. Alternatively, the control logic may be hard-coded into the controller 650. 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 658 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 600. The system control software 658 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 658 may be coded in any suitable computer readable programming language.

[0279] In some embodiments, the system control software 658 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 654 and / or memory device 656 associated with the system controller 650 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.

[0280] The substrate positioning program may include program code for process tool components used to load the substrate onto the pedestal 618 and control the spacing between the substrate and other parts of the process tool 600 .

[0281] 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 by, for example, adjusting throttle valves in the exhaust systems of the process stations, gas flows to the process stations, etc.

[0282] The heater control program may include code for controlling the current to a heating device 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.

[0283] The plasma control program may include code for setting RF power levels applied to process electrodes in one or more process stations in accordance with embodiments herein.

[0284] The pressure control program may include code for maintaining pressure in the reaction chamber according to embodiments herein.

[0285] In some embodiments, there may be a user interface associated with the system controller 650. 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.

[0286] In some embodiments, the parameters adjusted by the system controller 650 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.

[0287] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 650 from various process tool sensors. Signals for controlling the process can be output at analog and digital output connections of the process tool 600. 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.

[0288] The system controller 650 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 that operate the dry development and / or etching processes according to various embodiments described herein.

[0289] The system controller 650 may include 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. A machine-readable medium containing instructions for controlling process operations according to the disclosed embodiments may be coupled to the system controller 650.

[0290] In some implementations, the system controller 650 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 the operation of the system 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. Depending on the processing conditions and / or type of system, the system controller 650 may be programmed to control any of the processes disclosed herein, including delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow settings, fluid delivery settings, position and operation settings, tools and other transport tools connected or interlocked with the particular system, and / or wafer loading and unloading from load locks.

[0291] Broadly, the system controller 650 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 650 in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or to 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 during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0292] The system controller 650 may be part of, coupled to, or a combination of a computer that is integrated or coupled with the system or otherwise networked to the system in some embodiments. For example, the system controller 650 may be in the "cloud" or may be all or part of a fab host computer system, thereby enabling remote access of wafer processing. The computer may enable 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 up processing steps following a current process, or initiate a new process. In some embodiments, a remote computer (e.g., a server) may provide process recipes to the system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some embodiments, the system controller 650 receives instructions in the form of data, which 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 650 is configured to interface with or control. Thus, as described above, the system controller 650 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 be one in which one or more integrated circuits on the chamber are coupled to communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) to control the process on the chamber.

[0293] 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.

[0294] As described above, depending on the process step or steps being performed by the tool, the system controller 650 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 in a semiconductor manufacturing factory.

[0295] In certain embodiments, 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.

[0296] 7 illustrates generally a cross-sectional view of an inductively coupled plasma apparatus 700 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.

[0297] The inductively coupled plasma apparatus 700 includes an overall process chamber structurally defined by a chamber wall 701 and a window 711. The chamber wall 701 can be fabricated from stainless steel or aluminum. The window 711 can be fabricated from quartz or other dielectric materials. An optional internal plasma grid 750 divides the overall process chamber into an upper subchamber 702 and a lower subchamber 703. In most embodiments, the plasma grid 750 can be removed, thereby utilizing the chamber space consisting of the subchambers 702 and 703. A chuck 717 is positioned within the lower subchamber 703 near the bottom inner surface. The chuck 717 is configured to receive and hold a semiconductor wafer 719 on which etching and deposition processes are performed. The chuck 717, if present, can be an electrostatic chuck for supporting the wafer 719. In some embodiments, an edge ring (not shown) surrounds the chuck 717 and, if present on the chuck 717, has an upper surface that is approximately planar with an upper surface of the wafer 719. The chuck 717 also includes an electrostatic electrode for chucking and dechucking the wafer 719. For this purpose, a filter and DC clamp power supply (not shown) may be provided.

[0298] Other control systems for lifting the wafer 719 from the chuck 717 may also be provided. The chuck 717 may be charged using an RF power supply 723. The RF power supply 723 is connected to a matching circuit 721 through connection 727. The matching circuit 721 is connected to the chuck 717 through connection 725. In this manner, the RF power supply 723 is connected to the chuck 717. 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.

[0299] The elements for plasma generation include a coil 733 positioned over the window 711. In some embodiments, a coil is not used in the disclosed embodiments. The coil 733 is fabricated from a conductive material and includes at least one complete turn. The example coil 733 shown in FIG. 7 includes three turns. A cross section of the coil 733 is shown symbolically, with the coils with "X" rotating into the page and the coils with "●" rotating out of the page. The elements for plasma generation also include an RF power source 741 configured to provide RF power to the coil 733. Generally, the RF power source 741 is connected to a matching circuit 739 through connection 745. The matching circuit 739 is connected to the coil 733 through connection 743. In this manner, the RF power source 741 is connected to the coil 733. An optional Faraday shield 749 is positioned between the coil 733 and the window 711. The Faraday shield 749 may be maintained in a spaced apart relationship relative to the coil 733. In some embodiments, the Faraday shield 749 is disposed directly above the window 711. In some embodiments, the Faraday shield is between the window 711 and the chuck 717. In some embodiments, the Faraday shield is not maintained in a spaced apart relationship to the coil 733. For example, the Faraday shield may be directly below the window with no gap. The coil 733, the Faraday shield 749, and the window 711 are each configured to be substantially parallel to one another. The Faraday shield 749 may prevent metals or other species from depositing on the window 711 of the process chamber.

[0300] Process gases can flow into the process chamber through one or more main gas inlets 760 positioned in the upper subchamber 702 and / or through one or more side gas inlets 770. 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 740, 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 703 during an ALD purge operation. To selectively control the application of the vacuum environment provided by the vacuum pump, a valve controlled conduit can be used to fluidly connect the vacuum pump to the processing chamber. This can be done with 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.

[0301] During operation of the apparatus 700, one or more process gases may be supplied through the gas inlets 760 and / or 770. In certain embodiments, the process gases may be supplied only through the main gas inlet 760 or only through the side gas inlet 770. 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 749 and / or optional grid 750 may include internal channels and holes that allow delivery of process gases to the process chamber. Either or both of the Faraday shield 749 and optional grid 750 may function as showerheads to deliver process gases. In some embodiments, a liquid vaporization and delivery system may be positioned 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 760 and / or 770.

[0302] Radio frequency power is supplied from an RF power supply 741 to the coil 733, causing an RF current to flow through the coil 733. The RF current flowing through the coil 733 generates an electromagnetic field around the coil 733. The electromagnetic field generates an induced current in the upper subchamber 702. Physical and chemical interactions of the various generated ions and radicals with the wafer 719 etch features of the wafer 719 and selectively deposit layers on the wafer 719.

[0303] When a plasma grid 750 is used such that both an upper subchamber 702 and a lower subchamber 703 are present, induced currents act on the gas present in the upper subchamber 702, generating an electron-ion plasma in the upper subchamber 702. The optional internal plasma grid 750 limits the number of thermal electrons in the lower subchamber 703. In some embodiments, the apparatus 700 is designed and operated such that the plasma present in the lower subchamber 703 is an ion-ion plasma.

[0304] Both the upper electron-ion plasma and the lower ion-ion plasma may 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 may be removed from the lower subchamber 703 through port 722. The chuck 717 disclosed herein can be operated at elevated temperatures ranging from about 10 to 250° C. The temperature depends on the process operation and the particular recipe.

[0305] The apparatus 700 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 700 when installed in the intended fabrication facility. Additionally, the apparatus 700 may be coupled to a transfer chamber that allows a robot to load and unload semiconductor wafers into and out of the apparatus 700 using automated handling.

[0306] In some embodiments, a system controller 730 (which may include one or more physical or logical controllers) controls some or all of the operation of the process chamber. The system controller 730 may include one or more memory devices and one or more processors. In some embodiments, the apparatus 700 includes a switching system for controlling flow rates and durations when the disclosed embodiments are implemented. In some embodiments, the apparatus 700 can 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.

[0307] In some embodiments, the system controller 730 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 the operation of the system before, during, and after processing of a semiconductor wafer or substrate. The electronics may be integrated into the system controller 730 and control various components or subparts of the system or systems. Depending on the processing parameters and / or type of system, the system controller may be programmed to control any of the processes disclosed herein, including delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow settings, fluid delivery settings, position and operation settings, tools and other transport tools connected or interlocked with the particular system, and / or wafer loading and unloading from load locks.

[0308] Broadly, the system controller 730 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 end-point 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 to 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 during the fabrication or removal of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0309] The system controller 730 may, in some implementations, be part of a computer that is integrated or coupled with the system or otherwise networked to the system, or coupled to such a computer, or a combination thereof. For example, the controller may be in the "cloud" or may be all or part of a fab host computer system, thereby enabling remote access of wafer processing. The computer may enable 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 up processing steps following a current process, or initiate a new process. In some embodiments, a remote computer (e.g., a server) may provide process recipes to the system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some embodiments, the system controller 730 receives instructions in the form of data, which 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 730 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 be one in which one or more integrated circuits on the chamber are coupled to communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) to control the process on the chamber.

[0310] 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.

[0311] 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.

[0312] 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 that inserts and removes substrates for deposition and etching as described herein. Or, as described below, the EUVL patterning tool may be a module on a larger multi-component tool. FIG. 8 shows a semiconductor process cluster tool architecture with a vacuum integrated deposition, EUV patterning, and dry develop / etch module in conjunction with a vacuum transfer module suitable for carrying out the processes described herein. The process can be carried out without such vacuum integrated equipment, although such equipment may be advantageous in some implementations.

[0313] FIG. 8 illustrates a semiconductor process cluster tool architecture having a vacuum integrated deposition and patterning module in conjunction with a vacuum transfer module suitable for carrying out the processes described herein. The arrangement of transfer modules to "transport" 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, may also be included in the cluster.

[0314] A vacuum transport module (VTM) 838 interfaces with four processing modules 820a-820d, which can be individually optimized to perform various fabrication processes. By way of example, processing modules 820a-820d can be implemented to perform deposition, evaporation, ELD, dry develop, etch, strip, and / or other semiconductor processes. For example, module 820a 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 820b can be a PECVD tool, such as a Lam Vector®. It should be understood that the figures are not necessarily drawn to scale.

[0315] Airlocks 842 and 846, also known as loadlocks or transfer modules, interface with the VTM 838 and the patterning module 840. For example, as mentioned above, a suitable patterning module may be a TWINSCAN NXE:3300B® platform supplied by ASML of Veldhoven, The Netherlands. This tool architecture allows workpieces, such as semiconductor substrates or wafers, to be transferred under vacuum to prevent reaction prior to exposure. The integration of the deposition module with the lithography tool is achieved by H 2 O, O 2 This is facilitated by the fact that EUVL also requires significantly reduced pressures, given the strong optical absorption of incident photons by surrounding gases such as

[0316] 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 using a stand-alone EUVL scanner and deposition reactor, such as a Lam Vector tool, either stand-alone or integrated in a cluster architecture with other tools, such as etch, strip, etc. (e.g., a LamKiyo or Gamma tool), as a module, such as described with reference to FIG. 8, but without an integrated patterning module.

[0317] Airlock 842 may be an "out" load lock, referring to the transfer of substrates from the VTM 838 servicing deposition module 820a to the patterning module 840, and airlock 846 may be an "in" load lock, referring to the transfer of substrates from the patterning module 840 back to the VTM 838. The in load lock 846 may also provide an interface to the outside of the tool for the access and removal of substrates. Each process module has a facet that interfaces the module to the VTM 838. For example, deposition process module 820a has facet 836. Within each facet, sensors, such as sensors 1-18 shown, are used to detect the passage of wafer 826 as it moves between the respective stations. Patterning module 840 and airlocks 842 and 846 may similarly include additional facets and sensors not shown.

[0318] The main VTM robot 822 transfers wafers 826 between modules including airlocks 842 and 846. In one embodiment, the robot 822 has one arm, and in another embodiment, the robot 822 has two arms, each arm having an end effector 824 that lifts a wafer, such as wafer 826, for transfer. The front-end robot 844 is used to transfer wafers 826 from the outgoing airlock 842 to the patterning module 840 and from the patterning module 840 to the incoming airlock 846. The front-end robot 844 can also transfer wafers 826 between the incoming load lock and the exterior of the tool for access and unloading of substrates. Because the incoming airlock module 846 has the ability to adapt the environment between atmospheric pressure and vacuum, the wafers 826 can be moved between the two pressure environments without being damaged.

[0319] It should be noted that the EUVL tool may operate at a higher vacuum than the deposition tool. In this case, it is desirable to increase the vacuum environment of the substrate during transfer between the deposition tool and the EUVL tool to allow for outgassing of the substrate before entering the patterning tool. The unloading airlock 842 can provide this function by holding the transferred wafer at a low pressure, no higher than the pressure in the patterning module 840 for a period of time, and venting the off-gassing, so that the optics of the patterning tool 840 are not contaminated by off-gassing from the substrate. A suitable pressure for the venting off-gas airlock is 1E-8 Torr or less.

[0320] In some embodiments, the system controller 850 (which may include one or more physical or logical controllers) controls some or all of the operations in 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 850 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 the 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.

[0321] The system control software may include instructions for controlling the timing of application and / or extent of any aspect in 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.

[0322] In various embodiments, an apparatus for forming a negative pattern mask is provided. The apparatus may include a process chamber for patterning, deposition, and etching, and a controller including instructions for forming the negative pattern mask. The instructions may include code for patterning features in a chemically amplified (CAR) resist 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.

[0323] 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.

[0324] 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, although 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 process, system, 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 method using a resist, comprising the steps of: providing an organometallic precursor to a surface of a substrate in the presence of an organic co-reactant to provide a resist film; patterning the resist film by exposure to patterned radiation, thereby providing an exposed film having radiation-exposed and non-radiation-exposed areas; incubating the exposed film at a temperature of about 20-300° C., thereby providing an incubated film; and developing the incubated 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.

2. 2. The method of claim 1 , The method, wherein the resist film comprises an extreme ultraviolet (EUV) sensitive film.

3. 2. The method of claim 1 , The method, wherein the resist film comprises an organotin acetylide oxide, a tin acetylide oxide, a tin acetylide telluride, an organotin oxalate, a tin oxalate, an organotin formate, a tin formate, an organotin peroxide, or a tin peroxide.

4. 2. The method of claim 1 , The method wherein the dose-to-clear or dose-to-gel of the incubated membrane is lower than that of the exposed membrane.

5. 2. The method of claim 1 , The method, wherein the preparing comprises depositing a modifying precursor on a surface of the substrate to prepare the resist film, the modifying precursor being formed by reacting the organometallic precursor with the organic co-reactant.

6. 6. The method of claim 5, The method, wherein said depositing comprises depositing said modifying precursor in vapor form.

7. 2. The method of claim 1 , The patterning is performed at about 1 to 30 mJ / cm 2 The method includes a radiation dose of.

8. 2. The method of claim 1 , A method wherein said incubating comprises a temperature of about 100-250° C. in an ambient atmosphere for an optional time of about 30-300 seconds.

9. 2. The method of claim 1 , The method, wherein said incubating comprises a temperature of about 20-30° C. for a period of about 1-7 days.

10. 2. The method of claim 1 , A method wherein said incubating comprises a temperature of about 150-300° C. in an inert atmosphere, optionally with humidity, for an optional time of about 1-300 seconds.

11. 2. The method of claim 1 , The method, wherein said developing comprises wet developing or dry developing.

12. 12. The method of claim 11, A method wherein said wet development comprises water, an acid, a base, a ketone, an ester, an alcohol, an ether, or a combination thereof for an optional time of 15 to 60 seconds.

13. 13. The method of claim 12, The method, wherein said wet developing further comprises one or more surfactants.

14. 12. The method of claim 11, The dry development may be carried out with gaseous water, oxygen (O 2 ), a gaseous acid, a gaseous halide, or a combination thereof.

15. 2. The method of claim 1 , A method wherein said incubating comprises a temperature of about 100-250° C. in an ambient atmosphere and said developing comprises water in liquid or vapor form.

16. 2. The method of claim 1 , The incubation includes a temperature of about 20-30° C. for a period of about 1-7 days, and the developing includes the use of water, oxygen (O 2 ), a ketone or liquid water in conjunction with a dry development process comprising a gaseous acid, a gaseous halide, or a combination thereof.

17. 17. The method according to any one of claims 1 to 16, A method wherein the organometallic precursor comprises at least one ligand and the organic co-reactant displaces the at least one ligand to provide a modified precursor.

18. 20. The method of claim 17, The method, wherein the modified precursor comprises an increased or decreased carbon content compared to the organometallic precursor.

19. 20. The method of claim 17, The method, wherein said providing further comprises providing a molar ratio of said organometallic precursor to said organic co-reactant of from about 1000:1 to about 1:

4.

20. 20. The method according to any one of claims 1 to 19, The organometallic precursor has formula (I): M a R b L c (I) wherein M is a metal; 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 reactive with an organic co-reactant or counter reactant, 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. The method includes a structure having the following structure:

21. 21. The method of claim 20, The method wherein each R is L and / or M is tin (Sn).

22. 21. The method of claim 20, The method wherein each L is independently H, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy.

23. 23. The method of any one of claims 1 to 22, comprising: The method, wherein the organic co-reactant comprises one or more polymerizable moieties, alkynyl moieties, carbonyl moieties, dicarbonyl moieties, or haloalkyl moieties.

24. 24. The method of claim 23, The organic co-reactant has the formula (II): X 1 -Z-X 2 (II) (In the formula, X 1 and X 2 each is independently a leaving group; Z is carbonyl, dicarbonyl, optionally substituted alkylene, optionally substituted haloalkylene, optionally substituted alkenylene, or optionally substituted alkynylene. The method includes a structure having the following structure:

25. 20. The method of claim 17, The method, wherein the organometallic precursor and the organic co-reactant are provided in vapor form.

26. 20. The method of claim 17, The method, wherein said providing further comprises providing a corresponding reactant.

27. 27. The method of claim 26, The method wherein the corresponding reactant comprises oxygen or a chalcogenide precursor.

28. 17. The method according to any one of claims 1 to 16, The method, wherein the patterned radiation comprises EUV exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum atmosphere.

29. 17. The method according to any one of claims 1 to 16, The method, wherein said patterning further comprises releasing carbon dioxide and / or carbon monoxide from said exposed film.

30. 17. The method according to any one of claims 1 to 16, The method, wherein said patterning further comprises photopolymerization occurring within said exposed film.

31. An apparatus for forming a resist film, comprising: a deposition module including a chamber for depositing a resist film; a patterning module comprising a photolithography tool having a radiation source with a wavelength less than 300 nm; an incubation module including a chamber for incubating the resist film; a developing module including a chamber for developing the resist film; one or more memory devices, one or more processors, and machine readable instructions for causing, in the deposition module, deposition of a metalorganic precursor on an upper surface of a semiconductor substrate in the presence of an organic co-reactant to form the resist film; machine readable instructions for patterning, in the patterning module, the resist film by direct patterning radiation exposure at a resolution of less than 300 nm, thereby forming an exposed film having radiation exposed areas and radiation unexposed areas; machine readable instructions for incubating, in the incubating module, the exposed film at a temperature between about 20 and 300° C., thereby providing an incubated film; machine readable instructions for developing the incubated film in the developing module to remove the radiation exposed areas or the radiation unexposed areas to provide a pattern in the resist film; and a controller including system control software encoded with instructions including:

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

33. 33. The apparatus of claim 32, wherein the radiation source of the photolithography tool is a radiation source with a wavelength of less than 30 nm.

34. 34. The apparatus of claim 33, The apparatus, wherein the instructions comprising machine-readable instructions further comprise instructions for patterning, in the patterning module, the resist film directly by EUV exposure at a resolution of less than 30 nm, thereby forming the exposed film having EUV exposed areas and EUV non-exposed areas.

35. 34. The apparatus of claim 33, The apparatus, wherein the instructions including machine-readable instructions further include instructions for causing, in the developing module, development of the incubated film to remove the EUV exposed areas or the EUV non-exposed areas to provide a pattern in the resist film.

36. 34. The apparatus of claim 33, The apparatus, wherein the instructions comprising machine-readable instructions further comprise instructions for causing a change in a molar ratio of the organometallic precursor and the organic co-reactant in the deposition module to form the resist film.

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