Apparatus and process for EUV dry resist sensitization by gas phase infusion of a sensitizer

Abstract

This invention relates to stacks having sensitizing films, and methods and apparatus for coating such sensitizing films. In certain embodiments, the sensitizer may be provided in gaseous form, and unreacted sensitizer precursors may be recovered after the deposition step.

Description

Technical Field

[0001] This invention relates to stacks having sensitizing films, and methods and apparatus for coating such sensitizing films. In certain embodiments, the sensitizer may be provided in gaseous form, and unreacted sensitizer precursors may be recovered after the deposition step. Prior Technology

[0002] The background provided herein is for the purpose of outlining the technical context. The inventors’ work (within the scope described in the preceding paragraphs) and any descriptive features that may not have been otherwise considered prior art at the time of application are not expressly or impliedly acknowledged as prior art relative to this invention.

[0003] Thin-film patterning in semiconductor processing is often an important step in semiconductor manufacturing. Patterning involves lithography. In conventional lithography (e.g., 193 nm lithography), the pattern is printed by emitting photons from a photon source onto a mask and printing the pattern onto a photosensitive photoresist, thereby inducing a chemical reaction in the photoresist, which removes certain portions of the photoresist after development to form the pattern.

[0004] Advanced technology nodes (defined by the International Semiconductor Technology Roadmap) include nodes of 22 nm, 16 nm, and beyond. For example, in the 16 nm node, the width of a typical via or line in a damascene structure is typically no greater than about 30 nm. The miniaturization of features on advanced semiconductor integrated circuits (ICs) and other devices is driving lithography to improve resolution.

[0005] Extreme ultraviolet (EUV) lithography extends lithography techniques by moving to imaging source wavelengths smaller than those achievable with conventional lithography methods. EUV sources with wavelengths of approximately 10–20 nm or 11–14 nm (e.g., 13.5 nm) can be used in leading-edge lithography tools, also known as scanners. EUV radiation is strongly absorbed in a wide range of solid and fluid materials, including quartz and water vapor, and therefore can be operated in a vacuum. Summary of the Invention

[0006] This invention relates to the use of a sensitizing film disposed within a stack. In one example, the sensitizing film employs an EUV blocking material in combination with an EUV sensitizer. While the EUV blocking material may include one or more EUV-sensitive materials (e.g., any of those described herein), the EUV sensitizer may include one or more compounds that enhance EUV absorption, thus providing additional beneficial photoelectrons during EUV radiation. In this way, the EUV dose to the film can be reduced compared to the dose used for a stack without an EUV sensitizer.

[0007] In some embodiments, the EUV sensitizer comprises one or more EUV-absorbing compounds that thus provide favorable photoelectrons upon EUV irradiation, which can be injected into the membrane to provide further EUV-mediated lysis events. In this way, the EUV dose to the membrane can be reduced compared to the dose used for a stack without an EUV sensitizer.

[0008] Accordingly, in the first embodiment, the present invention is characterized by a stack comprising: a semiconductor substrate having a top surface; and a sensitizing film disposed on the top surface of the semiconductor substrate. In some embodiments, the film comprises an EUV resistive material, wherein an EUV sensitizer is dispersed throughout the film. In a particular embodiment, the EUV sensitizer is or comprises iodine or xenon. In other embodiments, the EUV sensitizer is I2, HI, or an organometallic precursor comprising an iodine-substituted alkyl group, or a precursor thereof, and any precursor described herein. In some embodiments, the EUV sensitizer is RI Sn(NR2)3, wherein RI is an alkyl group comprising one or more iodine-substituted alkyl groups as appropriate, and each R is independently an alkyl group. In other embodiments, the EUV sensitizer is 133Xe, 136Xe, 129Xe, or any combination of these isotopes.

[0009] In the second embodiment, the present invention is characterized by a stack comprising: a semiconductor substrate having a top surface; and a sensitizing film disposed on the top surface of the semiconductor substrate, wherein the film comprises an EUV resistive material and an EUV sensitizer containing xenon. In some embodiments, the EUV sensitizer is 133 Xe, 136 Xe, 129 Xe, or any combination of these isotopes.

[0010] In the third embodiment, the present invention is characterized by a method for forming a sensitized film, the method comprising: providing a semiconductor substrate in a chamber; and delivering an EUV resist material or a precursor thereof and an EUV sensitizer to the chamber. In some embodiments, the method thereby forms a sensitized film on the top surface of the semiconductor substrate.

[0011] In some embodiments, the EUV inhibitor material (or its precursor) and the EUV sensitizer may be delivered sequentially in any order. In other embodiments, the EUV inhibitor material (or its precursor) and the EUV sensitizer are delivered simultaneously. In still other embodiments, the EUV inhibitor material (or its precursor) and the EUV sensitizer are provided in gaseous form.

[0012] In other embodiments, the EUV sensitizer is provided as a driving gas for vapor containing EUV inhibitor material or its precursor.

[0013] In some embodiments, the delivery step further includes delivering one or more reactive substances to the chamber. In other embodiments, the EUV sensitizer is provided as a driving gas for one or more reactive substances.

[0014] In some embodiments, the EUV sensitizer is provided as a foaming gas, which is an EUV inhibitor material or a precursor thereof. In other embodiments, the EUV sensitizer is provided as a diluent delivered to the chamber.

[0015] In the fourth embodiment, the present invention is characterized by a method for forming a sensitized film, the method comprising: depositing a film comprising an EUV resistive material on a top surface of a semiconductor substrate; and heating the film in a chamber and in the presence of an EUV sensitizer in gaseous form (e.g., thus forming a sensitized film on the top surface of the semiconductor substrate). In a particular embodiment, the sensitized film comprises an EUV resistive material and an EUV sensitizer.

[0016] In some embodiments, the deposition step includes thermal atomic layer deposition, spin coating deposition, electron beam evaporation, or a combination thereof.

[0017] In the fifth embodiment, the present invention is characterized by a method for forming a sensitized film, the method comprising: providing a chamber containing at least a residual amount of EUV sensitizer; providing a semiconductor substrate within the chamber; and conveying an EUV resist material or a precursor thereof into the chamber (e.g., thereby forming a sensitized film on the top surface of the semiconductor substrate). In some embodiments, the sensitized film comprises an EUV resist material and an EUV sensitizer.

[0018] In the sixth embodiment, the present invention is characterized by an apparatus for depositing a sensitized film, the apparatus comprising: a deposition module including a chamber for depositing an EUV resist material and an EUV sensitizer as a sensitized film, wherein the EUV resist material or its precursor and the EUV sensitizer are provided in gaseous form. In some embodiments, the apparatus also includes: a patterning module including an EUV lithography tool having a radiation source with a wavelength of less than 30 nm; and / or a developing module including a chamber for developing the sensitized film.

[0019] In other embodiments, the device may include a controller having one or more memory devices, one or more processors, and system control software programmed to execute film deposition instructions. In some embodiments, the instructions include instructions for (e.g., in a deposition module) to deposit a sensitized film on the top surface of a semiconductor substrate, wherein the sensitized film includes an EUV resist material and an EUV sensitizer. In other embodiments, the instructions include (e.g., in a patterning module) to pattern the sensitized film at a resolution of less than 30 nm by direct EUV exposure in a vacuum environment with a wavelength range of about 10 nm to about 20 nm (e.g., thus forming a pattern within the sensitized film). In still other embodiments, the instructions include (e.g., in a developing module) to develop the sensitized film to provide the pattern within the sensitized film.

[0020] In some embodiments, according to instructions, EUV inhibitor materials or their precursors and EUV sensitizers may be delivered sequentially or simultaneously in any order.

[0021] In other embodiments, according to the instructions, the EUV sensitizer is provided as a driving gas for an EUV inhibitor material or a precursor thereof. In still other embodiments, the instructions further include (e.g., in a deposition module): delivering one or more reactive substances into a chamber, wherein the EUV sensitizer is provided as a driving gas for one or more reactive substances. In some embodiments, according to the instructions, the EUV sensitizer is provided as a foaming gas containing vapor of an EUV inhibitor material or a precursor thereof. In a further embodiment, according to the instructions, the EUV sensitizer is provided as a diluent delivered to a chamber in the deposition module.

[0022] In the seventh embodiment, the present invention is characterized by an apparatus for depositing a sensitized film, the apparatus comprising: a deposition module including a heater and a chamber for depositing an EUV resist material as a film. In some embodiments, the apparatus also comprises: a patterning module including an EUV lithography tool having an EUV lithography tool having a wavelength radiation source of less than 30 nm; a developing module including a chamber for developing the sensitized film; and / or a controller including one or more memory devices, one or more processors, and system control software programmed to execute film deposition instructions.

[0023] In some embodiments, the instructions include instructions for (e.g., in a deposition module) to deposit a film on the top surface of a semiconductor substrate and to heat the film using a heater in the presence of an EUV sensitizer in gaseous form, thereby forming a sensitized film on the top surface of the semiconductor substrate. In some embodiments, the sensitized film includes an EUV resistive material and an EUV sensitizer.

[0024] In other embodiments, the instructions include (e.g., in a patterning module): directly exposing the sensitized film in a vacuum environment using EUV with a wavelength range of about 10 nm to about 20 nm to pattern the sensitized film at a resolution of less than 30 nm, thereby forming a pattern within the sensitized film. In still other embodiments, the instructions include (e.g., in a developing module): developing the sensitized film to provide the pattern within the sensitized film.

[0025] In the eighth embodiment, the present invention is characterized by an apparatus for depositing a sensitized film, the apparatus comprising: a deposition module including a chamber for depositing an EUV resist material as a film, wherein the chamber includes at least a residual amount of EUV sensitizer. In some embodiments, the apparatus may further include: a patterning module including an EUV lithography tool having an EUV lithography tool having a wavelength radiation source of less than 30 nm; a developing module including a chamber for developing the sensitized film; and / or a controller including one or more memory devices, one or more processors, and system control software programmed to execute film deposition instructions.

[0026] In some embodiments, the instructions include (e.g., in a deposition module): depositing a sensitized film on the top surface of a semiconductor substrate, wherein the sensitized film includes an EUV resist material and an EUV sensitizer. In other embodiments, the instructions include (e.g., in a patterning module): patterning the sensitized film in a vacuum environment by direct EUV exposure in the wavelength range of about 10 nm to about 20 nm at a resolution of less than 30 nm, thereby forming a pattern within the sensitized film. In still other embodiments, the instructions include (e.g., in a developing module): developing the sensitized film to provide the pattern within the sensitized film.

[0027] In any of the embodiments herein, EUV exposure may have a wavelength of 13.5 nm.

[0028] In any embodiment herein, the device may include a recovery module having a trap, wherein the recovery module may be fluidly connected to the deposition module. In some embodiments, the device may include instructions that may further include (e.g., in the recovery module): capturing EUV sensitizer present in gaseous form within the chamber of the deposition module.

[0029] In any of the embodiments described herein, the EUV inhibitor material comprises an organometallic material (e.g., any of those described herein). In a particular embodiment, the organometallic material comprises tin. In other embodiments, the organometallic material further comprises, where appropriate, an iodine-substituted alkyl group (e.g., -NR2, wherein each R may be independently a substituted alkyl group, as described herein).

[0030] In any embodiment herein, the EUV inhibitor material or film may include any EUV-sensitive material described herein. In a particular embodiment, the material or film includes tin, its alloys, its oxides, or their complexed oxides.

[0031] In any of the embodiments herein, the EUV sensitizer may be provided in vapor form.

[0032] In any of the embodiments herein, the EUV sensitizer comprises or may be xenon or iodine. In some embodiments, the EUV sensitizer may be I2, HI, or an organometallic precursor comprising an iodine-substituted alkyl group (e.g., any of those described herein). In other embodiments, the EUV sensitizer may be 133Xe, 136Xe, 129Xe, or any combination of these isotopes.

[0033] In any of the embodiments herein, the relative reactants are oxygen-containing relative reactants, such as O2, O3, water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, dihydroxy alcohols, polyhydroxy alcohols, fluorodihydroxy alcohols, fluoropolyhydroxy alcohols, fluorodiols, formic acid, and other sources of hydroxyl moieties, and combinations thereof. Additional relative reactants may include any of those described herein.

[0034] In any of the embodiments herein, the sensitized film comprises a dry deposition inhibitor or a spin-coating inhibitor.

[0035] In any embodiment herein, the method further includes (e.g., after the transport step): patterning the sensitized film in a vacuum environment by EUV exposure in the wavelength range of about 10 nm to about 20 nm. In some embodiments, compared to a control film without the EUV sensitizer, the EUV exposure generates additional primary and / or secondary photoelectrons within the sensitized film.

[0036] In any embodiment herein, the method may include (e.g., after the delivery step and / or before the patterning step, if present): capturing the EUV sensitizer present in gaseous form within the chamber. In some embodiments, the capture step includes employing a cold trap to recover the gaseous EUV sensitizer. [ definition , ] [ , ]

[0037] As used interchangeably herein, "alkoxy" or "acetylated" refers to an alkoxy group, as defined herein, that is attached to a parent molecule group via an oxygen group. In certain embodiments, the alkoxy group is -OC(O)-Ak, where Ak is an alkyl group as defined herein. In some embodiments, the unsubstituted alkoxy group is a C2-7 alkoxy group. Exemplary alkoxy groups include acetylated groups.

[0038] "Alkenyl" refers to a C2-24 alkyl group having one or more double bonds, substituted as appropriate. Alkenyl groups can be cyclic (e.g., C3-24 cycloalkenyl) or acyclic. Alkenyl groups can also be substituted or unsubstituted. For example, an alkenyl group can be substituted with one or more substituents, as described herein with respect to alkyl groups. Unsubstituted alkenyl groups, not limited to this definition, include propenyl and vinyl groups.

[0039] "Alkenyl" refers to the polyvalent (e.g., divalent) form of an alkenyl group (which is a C2-24 alkyl group having one or more double bonds, substituted as appropriate). Alkenyl groups can be cyclic (e.g., C3-24 cycloalkenyl groups) or acyclic. Alkenyl groups can be substituted or unsubstituted. For example, alkenyl groups can be substituted with one or more substituents, as described herein with respect to alkyl groups. Exemplary non-limiting alkenyl groups include -CH=CH- or -CH=CHCH2-.

[0040] "Alkoxy" refers to -OR, where R is an alkyl group that is substituted as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, and trihaloalkoxy groups, such as trifluoromethoxy. Alkoxy groups may be substituted or unsubstituted. For example, an alkoxy group may be substituted with one or more substituents, as described herein with respect to alkyl groups. Exemplary unsubstituted alkoxy groups include C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, or C1-24 alkoxy groups.

[0041] "alkyl" and the prefix "alkane" refer to a branched or unbranched saturated hydrocarbon group having 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), sec-butyl (s-Bu), tert-butyl (t-Bu), cyclobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. Alkyl groups can be cyclic (e.g., C3-24 cycloalkyl) or acyclic. Alkyl groups can be branched or unbranched. Alkyl groups can also be substituted or unsubstituted. For example, alkyl groups can include haloalkyl groups, wherein the alkyl group is substituted with one or more halogen groups, as described herein. In another example, the alkyl group may be substituted with one, two, three, or four (in the case of an alkyl group having two or more carbons) substituents, the substituents being independently selected from the group consisting of: (1) C1-6 alkoxy (e.g., -O-Ak, where Ak is a C1-6 alkyl group substituted as appropriate); (2) amino (e.g., -NRN1 RN2, where each RN1 and RN2 is independently H or an alkyl group substituted as appropriate, or RN1 and RN2 together with their respective nitrogen atoms form a heterocyclic group); (3) aryl; (4) arylalkoxy (e.g., -O-Lk-Ar, where Lk is a divalent form of an alkyl group substituted as appropriate, and Ar is an aryl group substituted as appropriate); (5) aryl (e.g., -C(O)-Ar, where Ar is an aryl group substituted as appropriate); (6) cyano (e.g., -CN); (7) carboxylaldehyde (e.g., -C(O)H); (8) carboxyl (e.g., -CO2) (9) C3-8 cycloalkyl (e.g., a monovalent saturated or unsaturated non-aromatic cyclic C3-8 hydrocarbon group); (10) halogen (e.g., F, Cl, Br or I); (11) heterocyclic group (e.g., a 5, 6 or 7-membered ring containing one, two, three or four non-carbon heteroatoms (e.g., nitrogen, oxygen, phosphorus, sulfur or halogen), unless otherwise stated); (12) heterocyclic oxygen group (e.g., -O-Het, where Het is a heterocyclic group, as described herein); (13) heterocyclic acetyl group (e.g., -C(O)-Het, where Het is a heterocyclic group, as described herein); (14) hydroxyl group (e.g., -OH); (15) N-protected amino group; (16) nitro group (e.g., -NO2); (17) lateral oxygen group (e.g., =O); (18) -CO2 RA, where RA is selected from (a) C1-6 alkyl, (b) C4-18 The group consisting of aryl and (c) (C4-18 aryl)C1-6 alkyl groups (e.g., -Lk-Ar, where Lk is the divalent form of an alkyl group substituted as appropriate, and Ar is an aryl group substituted as appropriate);(19) -C(O)NRB RC, wherein each RB and RC is independently selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) (C4-18 aryl)C1-6 alkyl (e.g., -Lk-Ar, where Lk is the divalent form of an alkyl group that is substituted as appropriate, and Ar is an aryl group that is substituted as appropriate); and (20) -NRG RH, wherein each RG and RH is independently selected from (a) hydrogen, (b) N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl (e.g., an alkyl group that is substituted as appropriate with one or more double bonds), (e) C2-6 alkynyl (e.g., an alkyl group that is substituted as appropriate with one or more triple bonds), (f) C4-18 aryl, and (g) (C4-18 aryl)C1-6 The group consisting of alkyl groups (e.g., Lk-Ar, where Lk is a divalent form of an alkyl group substituted as appropriate, and Ar is an aryl group substituted as appropriate), (h) C3-8 cycloalkyl groups, and (i) (C3-8 cycloalkyl) C1-6 alkyl groups (e.g., -Lk-Cy, where Lk is a divalent form of an alkyl group substituted as appropriate, and Cy is a cycloalkyl group substituted as appropriate, as described herein), wherein in one embodiment, no two groups are bonded to the nitrogen atom group via a carbonyl group. The alkyl group may be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halogens or alkoxy groups). In some embodiments, the unsubstituted alkyl group is a C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, or C1-24 alkyl group.

[0042] "alkylene" refers to the polyvalent (e.g., divalent) form of an alkyl group, as described herein. Exemplary alkylenes include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene is a C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, C1-24, C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkylene. Alkylenes may be branched or unbranched. Alkylenes may also be substituted or unsubstituted. For example, an alkylene may be substituted with one or more substituents, as described herein with respect to alkyl groups.

[0043] "Alynyl" refers to a C2-24 alkyl group having one or more triple bonds, substituted as appropriate. The alkynyl group can be cyclic or acyclic, such as ethynyl, 1-propynyl, and the like. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substituents, as described herein with respect to alkyl groups.

[0044] "Imyynyl" refers to the polyvalent (e.g., divalent) form of an alkynyl group (which is a C2-24 alkyl group having one or more triple bonds, depending on substitution). Imyynyl groups can be cyclic or acyclic. They can be substituted or unsubstituted. For example, an alkynyl group can be substituted with one or more substituents, as described herein with respect to alkyl groups. Exemplary non-limiting alkynyl groups include -C≡C- or -C≡CCH2-.

[0045] "Amino" refers to -NRN1 RN2, where RN1 and RN2 are each independently H, substituted alkyl or substituted aryl, or RN1 and RN2 together with their respective nitrogen atoms form a heterocyclic group as defined herein.

[0046] "Aryl" refers to any group containing an aromatic group based on carbon, including, but not limited to, phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, and the like, including fused benzo-C4-8 Cycloalkyl groups (e.g., as defined herein), such as indanyl, tetrahydronaphthyl, fluorenyl, and the like. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group having at least one heteroatom incorporated into 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 containing an aromatic group that does not contain a heteroatom. Aryl groups can be substituted or unsubstituted. Aryl groups can be substituted with one, two, three, four, or five substituents, such as any of the alkyl groups described herein.

[0047] "Arylidene" refers to the polyvalent (e.g., divalent) form of an aryl group as described herein. Exemplary arylidenes include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylidene is a C4-18, C4-14, C4-12, C4-10, C6-18, C6-14, C6-12, or C6-10 arylidene. The arylidene may be branched or unbranched. The arylidene may also be substituted or unsubstituted. For example, the arylidene may be substituted with one or more substituents, as described herein with respect to alkyl or aryl groups.

[0048] "(aryl)(alkyl)" means including a divalent form of an aryl group as described herein, which is attached to an alkylene group or heteroalkylene group as described herein. In some embodiments, the (aryl)(alkyl) group is -L-Ar- or -L-Ar-L- or -Ar-L-, where Ar is an aryl group and each L is independently an alkylene group or heteroalkylene group substituted as appropriate.

[0049] "Carbonyl" refers to the -C(O)- group, which can also be represented as >C=O or -CO group.

[0050] "Carboxyl group" refers to the -CO2 H group.

[0051] "Carboxyalkyl" means alkyl group substituted with one or more carboxyl groups as defined herein.

[0052] "Carboxyaryl" refers to an aryl group as defined herein that has been substituted with one or more carboxyl groups as defined herein.

[0053] "Cyclic anhydride" refers to a 3-, 4-, 5-, 6-, or 7-membered ring (e.g., a 5-, 6-, or 7-membered ring) having a -C(O)-OC(O)- group within the ring, unless otherwise specified. The term "cyclic anhydride" also includes bicyclic, tricyclic, and tetracyclic groups, wherein any of the aforementioned rings is fused to one, two, or three rings independently selected from the group consisting of an aromatic ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring. Exemplary cyclic anhydrides include groups formed by removing one or more hydrogen atoms from succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, isochroman-1,3-dione, oxepanedione, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, naphthalic anhydride, and 1,2-cyclohexanedicarboxylic anhydride. Other exemplary cyclic anhydrides include dioxotetrahydrofuranyl and dioxodihydroisobenzofuranyl. The cyclic anhydride group may be substituted or unsubstituted. For example, the cyclic anhydride group may be substituted by one or more groups (including those described herein as heterocyclic groups).

[0054] "Cycloalkenyl" refers to a monovalent unsaturated nonaromatic or aromatic cyclic hydrocarbon group having three to eight carbon atoms (unless otherwise stated) with one or more double bonds. Cycloalkenyl groups may be substituted or unsubstituted. For example, cycloalkenyl groups may be substituted with one or more groups (including those described herein as alkyl groups).

[0055] "Cycloalkyl" means a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group of three to eight carbons (unless otherwise specified), and examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.]heptyl and the like. Cycloalkyl can also be substituted or unsubstituted. For example, a cycloalkyl can be substituted with one or more groups (including those described herein as alkyl).

[0056] "Halogen" refers to F, Cl, Br or I.

[0057] "Halogenated alkyl" means an alkyl group as defined herein that has been substituted with one or more halogens.

[0058] "Heteroalkyl" means an alkyl group as defined herein that contains one, two, three or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium or halogen).

[0059] "Heteroalkylene" means a divalent form of an alkyl group as defined herein, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halogens). Heteroalkylene can be substituted or unsubstituted. For example, a heteroalkylene can be substituted with one or more substituents, as described herein with respect to alkyl groups.

[0060] "Heterocyclic group" refers to a 3-, 4-, 5-, 6-, or 7-membered ring (e.g., 5-, 6-, or 7-membered ring) containing one, two, three, or four non-carbon heteroatoms (e.g., groups independently selected from nitrogen, oxygen, phosphorus, sulfur, selenium, or halogens), unless otherwise specified. 3-membered rings have zero to one double bond, 4- and 5-membered rings have zero to two double bonds, and 6- and 7-membered rings have zero to three double bonds. The term "heterocyclic group" also includes bicyclic, tricyclic, and tetracyclic groups, wherein any of the aforementioned heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of an aromatic ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, and the like. Heterocyclic compounds include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azacinyl, azapanyl, azaheptanyl, azapinyl, azatidinyl, and azatyl. ), aziridinyl, azirinyl, azocanyl, azoocinyl, azononyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinylbenzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolyl nyl), benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl ), benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazyl epinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsulfonylamine, benzylsulfinylamineBenzylsulfinyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclyl ooctyl), diazacyclobutadieneyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, di-hydrogenazineyl hydroazepinyl), dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydropyridyl, dihydroquinolinyl, dihydrothienylDihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxxiranyl, dioxenyl, dioxoxenyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithicyclohexyl anyl), dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl nyl), imidazolyl, indazolyl (e.g., 1H-indazole), indolenyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazoyl, isoindolyl inyl), isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidiniyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolylNaphthiridinyl, Naphthopyranyl, Naphthothiazolyl, Naphthothioxolyl, Naphthotriazolyl, Naphthoxindolyl, Naphthyridinyl, Octahydroisoquinolinyl, Oxabicycloheptyl, Oxauracil, Oxaadiazolyl, Oxaazinoyl nyl), oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanonyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzoisothiazolyl Oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, and more. Phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidinone), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinylPyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidyl yrrolidinyl), pyrrolidonyl (e.g., 2-pyrrolidinyl), pyrrolinyl, pyrrolizidinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinoxalinyl ring Quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl, piperidyl, tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl Tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiadiazinyl), thiadiazolyl, thianthrenyl, thianylThiainyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thietyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl (thiomorpholinyl), thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, uricyl, uridinyl, xanthenyl, xanthinyl, xanthionyl And similar compounds, as well as their modified forms (e.g., including one or more side oxygen groups and / or amino groups) and their salts. Heterocyclic groups may be substituted or unsubstituted. For example, heterocyclic groups may be substituted with one or more substituents, as described herein with respect to alkyl groups.

[0061] "Hydrocarbyl" refers to a monovalent group formed by removing hydrogen atoms from a hydrocarbon. Unsubstituted hydrocarbyl groups, without limitation, include alkyl, alkenyl, alkynyl, and aryl groups as defined herein, wherein these groups consist only of carbon and hydrogen atoms. Hydrocarbyl groups may be substituted or unsubstituted. For example, a hydrocarbyl group may be substituted with one or more substituents, as described herein with respect to alkyl groups. In other embodiments, any alkyl or aryl group herein may be substituted with a hydrocarbyl group as defined herein.

[0062] "Hydroxyl" refers to -OH.

[0063] "Hydroxyalkyl" means an alkyl group as defined herein that is substituted with one to three hydroxyl groups, provided that no more than one hydroxyl group is attached to a single carbon atom of the alkyl group, and examples include hydroxymethyl, dihydroxypropyl and the like.

[0064] "Hydroxyaryl" means an aryl group as defined herein that is substituted with one to three hydroxyl groups, provided that no more than one hydroxyl group is attached to a single carbon atom of the aryl group, and examples include hydroxyphenyl, dihydroxyphenyl and the like.

[0065] "isocyanato" refers to -NCO.

[0066] "Oxido" refers to the -O‒ group.

[0067] "Oxo" refers to the =O group.

[0068] "Phosphine" refers to trivalent or tetravalent phosphorus having a hydrocarbon moiety. In some embodiments, phosphine is a -PRP3 group, wherein each RP is independently H, an alkyl group substituted as appropriate, or an aryl group substituted as appropriate. The phosphine group may be substituted or unsubstituted. For example, the phosphine group may be substituted with one or more substituents, as described herein with respect to alkyl groups.

[0069] "Selenol" refers to the -SeH group.

[0070] "Tellurol" refers to the -TeH group.

[0071] "Thioisocyanato" refers to -NCS.

[0072] "Thiol" refers to the -SH group.

[0073] As used herein, the term "about" means + / - 10% of any of the stated values. As used herein, this term modifies any of the stated values, a range of values, or the endpoints of one or more ranges.

[0074] As used herein, the terms “top,” “bottom,” “upper,” “lower,” “above,” and “below” are used to provide relative relationships between structures. The use of these terms does not imply or require that a particular structure must be placed in a specific location within the equipment.

[0075] Other features and advantages of the present invention will become apparent from the following description and claims. Simple Explanation of the Diagram

[0076] Figures 1A-1C present schematic diagrams of non-limited stacks. (A) A stack including a non-limited sensitized film 102 is provided; (B) A schematic diagram of a non-limited precursor of an EUV sensitizer-incorporated inhibitor material is provided; and (C) A schematic diagram of a non-limited system forming the sensitized film is provided.

[0077] Figures 2A-2C present flowcharts of non-limiting methods using sensitized films. Provided are (A) a first non-limiting method 200, including 202 depositing a photoresist (PR) having an EUV sensitizer; (B) a second non-limiting method 220, including 222 depositing PR in the presence of an EUV sensitizer and 226 baking / pretreating the PR layer; and (C) a third non-limiting method 240, including 242 providing a chamber having residual EUV sensitizer and 244 depositing PR in the presence of the EUV sensitizer.

[0078] Figure 3 presents a schematic diagram of an embodiment of a process station 300 for dry development.

[0079] Figure 4 presents a schematic diagram of an embodiment of the multi-station processing tool 400.

[0080] Figure 5 presents a schematic diagram of an embodiment of an inductively coupled plasma device 500.

[0081] Figure 6 presents a schematic diagram of an embodiment of a semiconductor process cluster tool architecture 600. Implementation

[0082] This invention generally relates to the field of semiconductor processing. In a specific instance, the invention pertains to methods and apparatus for employing EUV photoresist in combination with an EUV sensitizer. In some embodiments, the processing of the EUV photoresist (e.g., an EUV-sensitive metal- and / or metal oxide-containing resist film) may include EUV patterning and EUV patterned film development to form a patterned mask.

[0083] Detailed reference is made to specific embodiments of the present invention herein. Examples of specific embodiments are shown in the accompanying drawings. Although the invention will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the invention to these specific embodiments. Rather, it is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the invention. In the following description, numerous specific details are set forth to provide a thorough understanding of the invention. The invention may be practiced without some or all of these specific details. In other instances, well-known process operations are not described in detail so as not to unnecessarily obscure the invention.

[0084] EUV lithography utilizes EUV resists patterned to form a mask for etching the underlying layer. The EUV resist can be a polymer-based chemically amplified resist (CAR) produced via a liquid-based spin coating technique. An alternative to CAR is a directly photo-patternable metal oxide film, such as those available from Inpria (Corvallis, Oregon), described in, for example, U.S. Patent Publications 2017 / 0102612, 2016 / 021660, and 2016 / 0116839, which, by reference and in this document, at least disclose photo-patternable metal oxide films. These films can be produced via spin coating or dry vapor deposition. Metal oxide films can be directly patterned in a vacuum environment via EUV exposure (i.e., without the use of different photoresists), providing a patterning resolution of less than 30 nm. For example, the disclosures in U.S. Patent No. 9,996,004, entitled "EUV PHOTOPATTERNING OF VAPOR-DEPOSITED METAL OXIDE-CONTAINING HARDMASKS" and / or International Application No. PCT / US19 / 31618 (published as International Publication No. WO2019 / 217749), filed on May 9, 2019, entitled "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS," which (at least regarding the composition, deposition, and patterning of directly photo-patternable metal oxide films to form EUV resist masks) are incorporated herein by reference. Generally speaking, patterning involves exposing an EUV resist to EUV radiation to form a light pattern in the resist, followed by development based on the light pattern to remove a portion of the resist to form a mask.

[0085] Directly photo-patternable EUV resists can be composed of or contain metals and / or metal oxides mixed within organic components. Metals / metal oxides hold promise due to their ability to enhance EUV photon absorption and generate secondary electrons, and / or to exhibit greater etch selectivity relative to the underlying film stack and device layers. To date, these resists have been developed using a wet (solvent) method, which requires transferring the wafer to a developer to expose it to a developing solvent, followed by drying and baking. This wet development step not only limits productivity but also causes line collapse due to the surface tension effect during solvent evaporation between small features. [ Sensitized film and its stacking , ] [ , ]

[0086] This invention relates to the use of sensitized films and describes various compounds for depositing such films. In a particular embodiment, the sensitized film is disposed on the top surface of a substrate, wherein the film comprises two components: an EUV inhibitor material and an EUV sensitizer. In a particular embodiment, the EUV sensitizer is dispersed throughout the film. In some embodiments, the EUV sensitizer is incorporated into a metal-containing precursor providing the EUV inhibitor material. Such incorporation may include bonds (e.g., covalent bonds) between the EUV sensitizer and the metal-containing precursor. In other embodiments, the concentration gradient of the EUV sensitizer within the film is constant or varies. Such sensitized films can be deposited in any useful manner, details of which are also described herein.

[0087] Figure 1A shows a non-limiting stack including a substrate 101 (e.g., a semiconductor substrate) having a top surface and a sensitizing film 102 disposed on the top surface of the substrate 101. The film may include any useful EUV-sensitive material (e.g., any of those described herein) or a photoresist (PR) in combination with any useful EUV sensitizer.

[0088] The sensitized film can be formed using any useful precursor that provides an EUV resisting material and an EUV sensitizer. Figure 1B provides a non-limiting precursor having an EUV resisting material (or a precursor thereof) with an EUV sensitizer bound to it. As can be seen, the precursor may include an organometallic material having an alkyl group (black) and multiple coordinating groups (gray). Furthermore, the alkyl group may bind the EUV sensitizer at the β position (left side of Figure 1B) or the α position (right side of Figure 1B). In some embodiments, the alkyl group may be released by an elimination reaction upon EUV exposure. Additional precursors for EUV sensitizers and EUV resisting materials are described herein.

[0089] The sensitized film may include any useful amount of sensitizer. In one embodiment, the amount of sensitizer provides a sensitized film that results in a decrease in EUV dose during patterning, compared to patterning in a film without sensitizer. Undesirably, the sensitized film may generate a unidirectional flux of primary and / or secondary photoelectrons entering the film, thus providing additional radiation for patterning the film. In one example, the thickness of the sensitized film may be, for example, from about 5 nm to about 200 nm.

[0090] Sensitized films can be deposited in any useful manner, as described herein. Non-limiting deposition techniques include atomic layer deposition (ALD) (e.g., thermal ALD and plasma-enhanced ALD (PE-ALD)), spin-coating deposition, physical vapor deposition (PVD) (including PVD co-sputtering), chemical vapor deposition (CVD), plasma-enhanced CVD (PE-CVD), low-pressure CVD (LP-CVD), sputtering deposition, electron beam deposition (including electron beam co-evaporation, etc.), or combinations thereof.

[0091] Figure 1C provides a non-limiting system for depositing sensitized films. As can be seen, the system may include a first deposition chamber 100 and a vapor delivery system for delivering a precursor 105 (as described herein) of an EUV inhibitor material and an optional relative reactant 106 (as described herein). Such delivery can be accomplished in any useful manner. In one example, a first propellant gas 102 is passed through the precursor 105, and a second propellant gas 103 is passed through the relative reactant 106 to provide the compound in vapor form. Alternatively, a foaming gas may be passed through the liquid precursor 105 or the liquid relative reactant 106, and the foaming gas having the precursor or relative reactant in vapor form may be delivered into the chamber 100. Furthermore, the vapor delivery system may employ one or more diluents, wherein a first diluent 101 is provided in gaseous form to dilute the gas stream carrying the precursor, and wherein a second diluent 104 is provided in gaseous form to dilute the gas stream carrying the relative reactant. Therefore, as can be seen, EUV sensitizers (or EUV sensitizer precursors) can be provided as driving gases 102, 103, bubbling gases and / or diluents 101, 104.

[0092] As shown in Figure 1C, after or during deposition, the exhaust gas within chamber 100 can be pumped out using pump 110 and collected using cold trap 120. The temperature of the cold trap can be optimized to separate the gaseous EUV sensitizer 124 from the effluent 122 containing residual compounds in liquid form. In this way, unreacted sensitizer can be recovered for possible reuse or storage. In one embodiment, the temperature of the trap is above the boiling point of the EUV sensitizer to be trapped and below the boiling points of other compounds in the effluent. For example, xenon has a boiling point of about -108°C, and the trap temperature is above -108°C (e.g., -60°C to -40°C), thus allowing the recovery of xenon in the gaseous phase.

[0093] The recovered sensitizer can be stored for immediate or later reuse. In one embodiment, the system may include using a first pump 130 to liquefy the EUV sensitizer from a gaseous form and store it as a liquid. In another embodiment, the system may include using a second pump 140 to deliver the recovered EUV sensitizer to a second-stage deposition chamber 150. Similar to the reagents provided in the first-stage deposition chamber 100, the system may include a vapor delivery system to deliver a precursor 155 (e.g., any of those described herein) and a relative reactant 156 (e.g., any of those described herein) of the EUV inhibitor material to chamber 150. In one example, a third propellant gas 152 is passed through the precursor 155 and a fourth propellant gas 153 is passed through the relative reactant 156 to provide the compound in vapor form. Alternatively, a foaming gas may be passed through the liquid precursor 155 or the liquid relative reactant 156, and the foaming gas having the precursor or relative reactant in vapor form may be delivered to chamber 150. In addition, the steam delivery system may employ a third diluent 151 to dilute the gas stream carrying the precursor, and a fourth diluent 154 to dilute the gas stream carrying the relative reactants. EUV sensitizers (or EUV sensitizer precursors) may be provided as driving gases 152, 153, bubbling gases, and / or diluents 151, 154. [ Methods for forming sensitized films , ] [ , ]

[0094] Non-limiting methods for forming sensitized films may include: depositing a film having an EUV sensitizer, patterning the film through the film to provide EUV exposed and EUV unexposed areas, and developing the film. Alternatively, the film may be deposited using only an EUV resist material or its precursor, followed by embedding the EUV sensitizer (or its precursor) during or after resist deposition. These methods may include any useful lithography, deposition, EUV exposure, development, and post-coating processes as described herein.

[0095] Figure 2A provides a non-limiting method 200 for forming a sensitized film, wherein the method includes 202 depositing photoresist and EUV sensitizer as a sensitized film on the top surface of a substrate, wherein the film also includes an EUV resist material. In some embodiments, the EUV resist material and / or EUV sensitizer are provided in gaseous form.

[0096] The method may further include 208 patterning the film through EUV exposure to produce a PR pattern and 212 developing the film, thereby providing the PR pattern within the film. In many embodiments of development, exposed areas (positive) or unexposed areas (negative) are removed. In some embodiments, development may include selective deposition on exposed or unexposed areas of the PR, followed by an etching operation.

[0097] Optional steps may be performed to further process the substrate and / or film. In one example, the method may include optional step 204 to clean the back surface or bevel of the substrate or remove edge beads of photoresist deposited in a previous step. Such cleaning or removal steps may be used to remove particles that may be present after the photoresist layer has been deposited. In another example, the method may include optional step 206 to perform post-coat bake (PAB) on the deposited photoresist layer, thereby removing residual moisture from the layer to form a film; or pre-treating the photoresist layer in any useful manner. In yet another example, the method may include optional step 210 to perform post-exposure bake (PEB) on the exposed photoresist layer, thereby further removing residual moisture from the layer or promoting chemical condensation within the film; or post-treating the photoresist layer in any useful manner. In yet another example, the method may include optional step 203 to capture EUV sensitizers after deposition step 202. Additional post-coat processes are described herein, and any of these processes may be performed as optional steps to any of the methods described herein.

[0098] EUV sensitizers can be introduced at any useful stage before, during, or after deposition. In one example, deposition may include the use of both EUV inhibitor material and EUV sensitizer precursors within a deposition chamber. These precursors may be provided in the chamber, wherein the EUV sensitizer is provided as a propellant gas, a foaming gas, or a diluent. In yet another example, an existing EUV sensitizer is provided to the deposition chamber, which may then be embedded within the membrane during the deposition of the EUV inhibitor material. In certain embodiments, the EUV sensitizer is, for example, covalently bonded to the EUV inhibitor material precursor; and the resulting compound is provided in the form of vapor carried by the propellant gas or foaming gas.

[0099] In another example, the EUV sensitizer is provided after the resist deposition, for example through a post-processing step using the photoresist layer in the presence of the EUV sensitizer or its precursor. Such post-processing may include baking the PR layer in the presence of the EUV sensitizer (e.g., provided in gaseous form).

[0100] Figure 2B provides a non-limiting method 220 for forming a sensitized film, wherein the method includes 222 depositing PR as a resist film on the top surface of a substrate and 226 performing PAB or pretreatment in the presence of an EUV sensitizer or its precursor. In this manner, the EUV sensitizer can be used to dope the underlying film, thus providing a sensitized film. The method may further include 228 patterning the film by EUV exposure to provide a PR pattern and 232 developing the film, thus providing a PR pattern within the film.

[0101] Figure 2C provides another non-limiting method 240 for forming a sensitized film, wherein the method includes 242 providing a chamber with a residual EUV sensitizer or a precursor thereof, and 244 depositing PR as a resist film on the top surface of a substrate, thereby allowing the residual EUV sensitizer to be contained in the film during deposition to provide a sensitized film. The method may further include 250 patterning the film through EUV exposure to provide a PR pattern and 254 developing the film, thereby providing a PR pattern within the film.

[0102] As shown in Figures 2B-2C, optional steps can be performed, including steps 224 and 246, cleaning the back surface or bevel of the substrate or removing edge beads of PR deposited in previous steps; step 248, performing PAB on the deposited PR layer to remove residual moisture from the layer to form a film or to pre-treat the PR layer in any useful manner; steps 230 and 252, performing PEB on the exposed PR layer to further remove residual moisture from the layer or to promote chemical condensation within the film or to post-treat the PR layer in any useful manner; and / or steps 223 and 245, capturing unreacted EUV sensitizer after deposition 222 and 244.

[0103] Any useful type of chemicals may be used during the deposition and / or development steps. These steps may be based on dry processes using vapor-phase chemicals or wet processes using wet-phase chemicals. Many embodiments include combining all dry operations of vapor deposition, (EUV) photolithography, dry stripping, and dry development. Many other embodiments include dry processing operations as described herein that are advantageously combined with wet processing operations, such as spin-coating EUV photoresist (wet process) (e.g., available from Inpria) which may be combined with dry development or other wet or dry processes as described herein. In many embodiments, wafer cleaning may be a wet process as described herein, while other processes are dry processes. In still other embodiments, a wet development process may be used. [ EUV , ] [ Sensitizer , ] [ , ]

[0104] EUV sensitizers can be any useful compound that enhances light absorption. In some embodiments, the compound has a light absorption cross-section of about 9E+04 cm² / g to about 1.2E+05 cm² / g (e.g., at 93.4 eV or at 92 eV, which relates to EUV light absorption of about 13.5 nm).

[0105] In one embodiment, the EUV sensitizer is provided in gaseous form. In other embodiments, the compound is characterized by providing a gaseous density at standard temperature and pressure, for example, a density of less than about 5 g / cm³ or a density of about 0.002 g / cm³ to about 5 g / cm³. In a particular embodiment, the EUV sensitizer has a light absorption cross-section of about 9E+04 cm² / g to about 1.2E+05 cm² / g (e.g., at 93.4 eV) and a density of about 0.002 g / cm³ to about 5 g / cm³ at standard temperature and pressure.

[0106] Non-limiting EUV sensitizers may include any compound having or being Xe or I. Any useful isotopes of Xe and I may be used. In certain embodiments, the EUV sensitizer is 133Xe, 136Xe, or 129Xe. In other embodiments, two or more isotopes are used in combination. In other embodiments, the EUV sensitizer is formed by using an iodine-containing precursor (e.g., RI Sn(NR2)3), wherein RI is a optionally substituted alkyl group including one or more iodines, and each R is independently an alkyl group. In some embodiments, the iodine-containing precursor is (1-iodoisopropyl)tris(dimethylamino)tin, (2-iodoisopropyl)tris(dimethylamino)tin, (2-iodoisopropyl)tris(dimethylamino)tin, (2-iodobutyl, 1-(tris(dimethylamino)tin)), or (3-iodobutyl, 1-(tris(dimethylamino)tin)).

[0107] In some embodiments, the EUV sensitizer is formed by using an iodine-containing precursor, such as I2, HI, an organometallic precursor containing an iodine-substituted alkyl group, or further including any metal-containing precursor described herein that is iodine-substituted. In certain embodiments, the metal-containing precursor having iodine may include any of the formulas described herein (e.g., formulas (I), (II), (IIa), (III), (IV), (V), (VI), (VII), or (VIII), wherein at least one X is I, at least one R is an iodine-substituted alkyl group (e.g., an α-substituted alkyl group or a β-substituted alkyl group), and / or at least one L includes an iodine atom. In some embodiments, the iodine-substituted alkyl group (e.g., for R or as used in L) may be methyl, ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl, tert-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n-pentyl, or n-hexyl or a derivative thereof having one or more iodine substitutions. The iodine-substituted alkyl group may be a C1-10 alkyl group including one, two, three, four, or more iodine substitutions. In other embodiments, L may be iodine, an iodine-substituted alkyl group (e.g., any of those described herein), or an amino group (e.g., -NR1R2, wherein R1 and R2...). Each can be H or alkyl, such as any of those described herein, and wherein at least one of R1 or R2 comprises an iodine-substituted alkyl, alkoxy (e.g., -OR, where R is an iodine-substituted alkyl), or any organic moiety comprising one or more iodine-substituted moieties.

[0108] Other metal-containing precursors containing iodine may be SnI4, (CH3)3SnI, triisopropyl(methyl(iodo)ethyl)stanane, tri(dimethylamino)(methyl(iodo)ethyl)stanane, or tri(dimethylamino)(1-methyl-2-iodo-ethyl)stanane. In other embodiments, the metal-containing precursor may be Sn(NR2)4, SnR(NR2)3, SnR2(NR2)2, or SnR3(NR2), wherein each R is independently methyl, ethyl, n-propyl, or isopropyl, and at least one R is an iodine-substituted methyl, ethyl, n-propyl, or isopropyl group (e.g., having one or more iodine substitutions).

[0109] EUV sensitizers or their precursors may be provided in any useful form. In one embodiment, the EUV sensitizer or its precursor is provided in gaseous form. In a particular embodiment, the EUV sensitizer or its precursor is provided as a vapor in an inert carrier gas (e.g., iodine vapor or xenon vapor stream in N2). Non-limiting carrier gases include, for example, H2, He, Ar, or N2. In other embodiments, the EUV sensitizer or its precursor is provided itself as a gas (e.g., as I2 or Xe). EUV sensitizers or their precursors may also be provided as plasma (e.g., RF plasma as described herein or any other plasma condition), which can be used to generate reactive species (e.g., reactive I2, reactive atomic I species, reactive Xe, or reactive atomic Xe species). [ EUV , ] [ Inhibitor materials , ] [ , ]

[0110] The methods described herein may include any useful EUV resist material to provide a sensitized film (e.g., an imaging layer). EUV resist materials may be composed of or comprise of: metals (e.g., tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), or indium (In)); metal oxides, such as tin oxide (e.g., SnO2), tellurium oxide (e.g., TeO2), bismuth oxide (e.g., Bi2O3), antimony oxide (e.g., Sb2O3), or indium oxide (e.g., In2O3); alloys, such as tin alloys (e.g., tin telluride alloys), antimony telluride alloys (e.g., Sb2Te3), bismuth telluride alloys (e.g., Bi2Te3), or tin-bismuth alloys (including alloys having 60% or more tin); or combinations thereof. In some embodiments, the EUV resist material comprises an organometallic oxide (e.g., RM(MO)n, where M is a metal and R is an organic moiety having one or more carbon atoms, such as in an alkyl, alkylamino, or alkoxy group).

[0111] EUV inhibitor materials may be formed, as appropriate, in the presence of one or more relative reactants by using one or more metal-containing precursors. In certain embodiments, the metal-containing precursors include one or more ligands (e.g., unstable ligands) that can be removed or cleaved by EUV radiation. Furthermore, the precursors may be deposited (e.g., using any of the deposition processes described herein) and optionally treated (e.g., baking, processing, annealing, exposure to plasma, etc.) to provide a metal oxide layer (e.g., a layer comprising a metal oxide bonded network, which may include other nonmetallic and non-oxygen groups).

[0112] Non-metallic precursors may include metal halides, covering agents, or organometallic agents. In the precursor, the metal (or M) may be any metal having a high EUV absorption cross section (e.g., equal to or greater than 1 x 10⁷ cm² / mol).

[0113] The layers described herein (e.g., imaging layers, resistive films, and / or sensitizing films) may include elements (e.g., metal or non-metal atoms) having a high light absorption cross-section (e.g., equal to or greater than 1 x 10⁷ cm² / mol). These elements may be provided to provide the layer by depositing one or more precursors.

[0114] These layers (alone or together) can be considered as a membrane. In some embodiments, the membrane is a radiation-sensitive membrane (e.g., an EUV-sensitive membrane). This membrane can also function as an EUV inhibitor, as further described herein. In certain embodiments, the layer or membrane may include one or more ligands (e.g., EUV-unstable ligands) that can be removed, cleaved, or crosslinked by radiation (e.g., EUV or DUV radiation).

[0115] The precursor can provide a radiation-sensitive patternable film (or a patterned radiation-sensitive film or a photo-patternable film). Such radiation may include EUV radiation, DUV radiation, or UV radiation, provided by irradiating through a patterned mask, and is therefore patterned radiation. The film itself can be altered by exposure to such radiation, making the film radiation-sensitive or photosensitive. In a particular embodiment, the precursor is an organometallic compound comprising at least one metal center.

[0116] The precursor may have any useful number and type of ligands. In some embodiments, the ligands are characterized by their ability to react in the presence of a relative reactant or in the presence of patterned radiation. For example, the precursor may include ligands that react with the relative reactant, which may introduce bonds (e.g., -O-links) between metal centers. In another instance, the precursor may include ligands that are eliminated in the presence of patterned radiation. Such EUV-unstable ligands may include branched or straight-chain alkyl groups having β-hydrogen, and any of those described herein with respect to R in formula (I) or (II). In some embodiments, the EUV-unstable ligand (e.g., R in formula (I) or (II)) includes iodine.

[0117] The precursor can be any useful metal-containing precursor, such as an organometallic agent, a metal halide, or a covering agent (e.g., as described herein). In non-limiting instances, the precursor includes a structure having formula (I): Ma Rb (I), in: M is a metal or atom with a high EUV absorption cross section; Each R is independently H, halogen, substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted alkenyl, substituted alkynyl, substituted alkoxy, substituted alkoxy, substituted aryl, substituted amino, substituted bis(trialkylsilyl)amino, substituted trialkylsilyl, oxo, anionic ligand, neutral ligand, or polydentate ligand; a≥1; and b≥1.

[0118] In another non-limiting instance, the precursor includes a structure having formula (II): Ma Rb Lc (II), in: M is a metal or atom with a high EUV absorption cross section; Each R is independently a halogen, an alkyl group substituted as appropriate, an aryl group substituted as appropriate, an amino group substituted as appropriate, an alkoxy group substituted as appropriate, or L; Each L is independently a ligand, an anionic ligand, a neutral ligand, a polydentate ligand, an ionic ligand, or other part that is reactive with the relative reactant, wherein R and L together with M may, depending on the situation, form a heterocyclic group or wherein R and L together may, depending on the situation, form a heterocyclic group; a≥1; b≥1; and c≥1.

[0119] In some embodiments, each ligand in the precursor may be a ligand reactive with the relative reactant. In one example, the precursor comprises a structure having formula (II), wherein each R is independently L. In another example, the precursor comprises a structure having formula (IIa): Ma Lc (IIa), in: M is a metal or atom with a high EUV absorption cross section; Each L can be independently a ligand, an ion, or another part that is reactive with the relative reactant, wherein two Ls together may, depending on the situation, form a heterocyclic group; a≥1; and c≥1. In a particular embodiment of formula (IIa), a is 1. In a further embodiment, c is 2, 3, or 4.

[0120] For any of the formulas herein, M can be a metal or metalloid or atom having a highly patterned radiation absorption cross section (e.g., an EUV absorption cross section equal to or greater than 1 x 10⁷ cm² / mol). In some embodiments, M is tin (Sn), bismuth (Bi), tellurium (Te), cesium (Cs), antimony (Sb), indium (In), molybdenum (Mo), hafnium (Hf), iodine (I), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), platinum (Pt), and lead (Pb). In further embodiments, in formulas (I), (II), or (IIa), M is Sn, a is 1, and c is 4. In other embodiments, in formulas (I), (II), or (IIa), M is Sn, a is 1, and c is 2. In certain embodiments, M is Sn(II) (e.g., in formula (I), (II), or (IIa)), and is thus provided as a precursor of a Sn(II)-based compound. In other embodiments, M is Sn(IV) (e.g., in formula (I), (II), or (IIa)), and is thus provided as a precursor of a Sn(IV)-based compound. In certain embodiments, the precursor comprises iodine (e.g., in periodate, iodine-substituted alkyl, or iodine-substituted amino groups).

[0121] For any formula herein, each R is independently H, a halogen, an alkyl group with optional substitution, a cycloalkyl group with optional substitution, a cycloalkenyl group with optional substitution, an alkenyl group with optional substitution, an alkoxy group with optional substitution (e.g., -OR1, where R1 may be an alkyl group with optional substitution), an alkoxy group with optional substitution, an aryl group with optional substitution, an amino group with optional substitution, a bis(trialkylsilyl)amino group with optional substitution, a trialkylsilyl group with optional substitution, a slant group (oxo), an anionic ligand (e.g., oxido, chloride, hydrido, acetate, iminodiacetate, propionate, butyrate, benzoate, etc.), a neutral ligand, or a polydentate ligand. In some embodiments, R is iodine or iodinated.

[0122] In some embodiments, the substituted amino group is -NR1R2, wherein each R1 and R2 is independently H or an alkyl group; or wherein R1 and R2 together with their respective attached nitrogen atoms form a heterocyclic group as defined herein. In other embodiments, the substituted bis(trialkylsilyl)amino group is -N(SiR1R2R3)2, wherein each R1, R2, and R3 is independently an substituted alkyl group. In still other embodiments, the substituted trialkylsilyl group is -SiR1R2R3, wherein each R1, R2, and R3 is independently an substituted alkyl group. In some embodiments, R1 and / or R2 is iodine or iodine-substituted.

[0123] In other embodiments, the formula includes a first R (or a first L) of -NR1 R2 and a second R (or a second L) of -NR1 R2, wherein each R1 and R2 is independently H or an alkyl group substituted as appropriate; or wherein R1 from the first R (or the first L) and R1 from the second R (or the second L), together with their respective attached nitrogen and metal atoms, form a heterocyclic group as defined herein. In still other embodiments, the formula includes a first R of -OR1 and a second R of -OR1, wherein each R1 is independently H or an alkyl group substituted as appropriate; or wherein R1 from the first R and R1 from the second R, together with their respective attached oxygen and metal atoms, form a heterocyclic group as defined herein.

[0124] In some embodiments, at least one of R or L (e.g., in formula (I), (II), or (IIa)) is an alkyl group that is substituted as appropriate. Non-limiting alkyl groups include, for example, CnH2n+1, where n is 1, 2, 3, or greater, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl. In many embodiments, R or L has at least one β-hydrogen or β-fluorine or β-iodine. In other embodiments, at least one of R or L is a halogen-substituted alkyl group (e.g., a fluorine-substituted alkyl group and / or an iodine-substituted alkyl group).

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

[0126] In some embodiments, each R or L, or at least one R or L (e.g., in formula (I), (II), or (IIa)), may contain a nitrogen atom. In particular embodiments, one or more R or L may be an optional substituted amino group, an optional substituted monoalkyl amino group (e.g., -NR1H, where R1 is an optional substituted alkyl group), an optional substituted dialkyl amino group (e.g., -NR1R2, where each R1 and R2 is independently an optional substituted alkyl group), or an optional substituted bis(trialkylsilyl) amino group. Non-limiting R and L substituents may include, for example, -NMe2, -NHMe, -NEt2, -NHEt, -NMeEt, -N(t-Bu)-[CHCH3]2, -N(t-Bu)-(tbba), -N(SiMe3)2, and -N(SiEt3)2.

[0127] In some embodiments, each R or L, or at least one R or L (e.g., in formula (I), (II), or (IIa)), may contain a silicon atom. In particular embodiments, one or more R or L may be a trialkylsilyl group substituted as appropriate, or a bis(trialkylsilyl)amino group substituted as appropriate. Non-limiting R or L substituents may include, for example, -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2.

[0128] In some embodiments, each R or L, or at least one R or L (e.g., in formula (I), (II), or (IIa)), may contain an oxygen atom. In particular embodiments, one or more R or L may be an alkoxy group substituted as appropriate, or an alkoxy group substituted as appropriate. Non-limiting R or L substituents include, for example, methoxy, ethoxy, isopropoxy (i-PrO), tert-butoxy (t-BuO), acetate (-OC(O)-CH3), and -O=C(CH3)-CH=C(CH3)-O-(acac).

[0129] Any formula in this document may contain one or more neutral ligands. Non-limiting neutral ligands include, as appropriate, substituted amino groups (e.g., NR3 or R2 N-Ak-NR2, wherein each R may be independently H, as appropriate, substituted alkyl, as appropriate, or substituted aryl, and Ak is as appropriate, substituted alkylene), as appropriate, substituted phosphine (e.g., PR3 or R2 P-Ak-PR2, wherein each R may be independently H, as appropriate, substituted alkyl, as appropriate, or substituted aryl, and Ak is as appropriate, substituted alkylene), as appropriate, substituted ether (e.g., OR2, wherein each R may be independently H, as appropriate, substituted alkyl, as appropriate, or substituted aryl), as appropriate, substituted alkyl, as appropriate, substituted alkyne, as appropriate, substituted benzene, oxy, or carbon monoxide.

[0130] Any formula in this document may contain one or more multidentate (e.g., bidentate) ligands. Non-limited polydentate ligands include diketo groups (e.g., acetoacetone (acac) or -OC(R1)-Ak-(R1)CO- or -OC(R1)-C(R2)-(R1)CO-), didentate diazonium groups (e.g., -N(R1)-Ak-N(R1)- or -N(R3)-CR4-CR2=N(R1)-), aromatic groups (e.g., -Ar-), amidinate groups (e.g., -N(R1)-C(R2)-N(R1)-), aminoalkoxy groups (e.g., -N(R1)-Ak-O- or -N(R1)2-Ak-O-), and diazadienyl groups (e.g., -N(R1)-C(R2)-C(R2)-N(R1)-). R1 is cyclopentadienyl, pyrazolate, a heterocyclic group substituted as appropriate, an alkylene group substituted as appropriate, or a heteroalkylene group substituted as appropriate. In a particular embodiment, each R1 is independently H, an alkyl group substituted as appropriate, a haloalkyl group substituted as appropriate, or an aryl group substituted as appropriate; each R2 is independently H or an alkyl group substituted as appropriate; R3 and R4 together form a heterocyclic group substituted as appropriate; Ak is an alkylene group substituted as appropriate; and Ar is an arylene group substituted as appropriate.

[0131] In a particular embodiment, the precursor includes tin. In some embodiments, the tin precursor includes SnR or SnR2 or SnR4 or R3 SnSnR3, wherein each R is independently H, halogen, a C1-12 alkyl group substituted as appropriate, a C1-12 alkoxy group substituted as appropriate, an amino group substituted as appropriate (e.g., -NR1 R2), a C2-12 alkenyl group substituted as appropriate, a C2-12 alkynyl group substituted as appropriate, a C3-8 cycloalkyl group substituted as appropriate, an aryl group substituted as appropriate, a cyclopentadienyl group substituted as appropriate, a bis(trialkylsilyl)amino group substituted as appropriate (e.g., -N(SiR1 R2 R3)2), an alkoxy group substituted as appropriate (e.g., acetate), a diketo group (e.g., -OC(R1)-Ak-(R2)CO-), or a bis(R1)-ak-N(R1)-. In certain embodiments, each R1, R2, and R3 is independently H or a C1-12 alkyl group (e.g., methyl, ethyl, isopropyl, tert-butyl, or neopentyl); and Ak is a C1-6 alkylene group substituted as appropriate. In certain embodiments, each R is independently a halogen, a C1-12 alkoxy group substituted as appropriate, an amino group substituted as appropriate, an aryl group substituted as appropriate, a cyclopentadienyl group, or a diketone group.Non-limited tin precursors include SnF2, SnH4, SnBr4, SnCl4, SnI4, tetramethyltin (SnMe4), tetraethyltin (SnEt4), trimethyltin chloride (SnMe3Cl), dimethyltin dichloride (SnMe2Cl2), methyltin trichloride (SnMeCl3), tetraallyltin, tetravinyltin, hexaphenylditin (IV) (Ph3 Sn-SnPh3, where Ph is phenyl), dibutyldiphenyltin (SnBu2Ph2), trimethyl(phenyl)tin (SnMe3Ph), trimethyl(phenylethynyl)tin, tricyclohexyltin hydride, tributyltin hydride (SnBu3H), dibutyltin diacetate (SnBu2(CH3COO)2), acetoacetone tin (II) (Sn(acac)2), SnBu3(OEt), SnBu2 (OMe)2, SnBu3 (OMe), Sn(t-BuO)4, Sn(n-Bu)(t-BuO)3, Tetra(dimethylamino)tin (Sn(NMe2)4), Tetra(ethylmethylamino)tin (Sn(NMeEt)4), Tetra(diethylamino)tin (IV)(Sn(NEt2)4), (dimethylamino)trimethyltin (IV)(Sn(Me)3 (NMe2), Sn(i-Pr)(NMe2)3, Sn(n-Bu)(NMe2)3, Sn(s-Bu)(NMe2)3, Sn(i-Bu)(NMe2)3, Sn(t-Bu)(NMe2)3, Sn(t-Bu)2 (NMe2)2, Sn(t-Bu)(NEt2)3 Sn(tbba), Sn(II)(1,3-bis(1,1-dimethylethyl)-4,5-dimethyl-(4R,5R)-1,3,2-diazastannolidin-2-ylidene)(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(SiMe3)2]2).

[0132] In other embodiments, the precursor includes bismuth, for example in BiR3, wherein each R is independently a halogen, a C1-12 alkyl group substituted as desired, a mono-C1-12 alkylamino group (e.g., -NR1H), a di-C1-12 alkylamino group (e.g., -NR1R2), an aryl group substituted as desired, a bis(trialkylsilyl)amino group substituted as desired (e.g., -N(SiR1R2R3)2), or a diketone group (e.g., -OC(R4)-Ak-(R5)CO-). In specific embodiments, each R1, R2, and R3 is independently a C1-12 alkyl group (e.g., methyl, ethyl, isopropyl, tert-butyl, or neopentyl); each R4 and R5 is independently H or a C1-12 alkyl group substituted as desired (e.g., methyl, ethyl, isopropyl, tert-butyl, or neopentyl). Non-limited bismuth precursors include BiCl3, BiMe3, BiPh3, Bi(NMe2)3, Bi[N(SiMe3)2]3, and Bi(thd)3, where thd is 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0133] In other embodiments, the precursor includes tellurium, such as TeR2 or TeR4, wherein each R is independently a halogen, a C1-12 alkyl group substituted as appropriate (e.g., methyl, ethyl, isopropyl, tert-butyl, and neopentyl), a C1-12 alkoxy group substituted as appropriate, an aryl group substituted as appropriate, a hydroxyl group substituted as appropriate, a side-oxyl group substituted as appropriate, or a trialkylsilyl group substituted as appropriate. Non-limited tellurium precursors include dimethyl tellurium (TeMe2), diethyl tellurium (TeEt2), di(n-butyl) tellurium (Te(n-Bu)2), di(isopropyl) tellurium (Te(i-Pr)2), di(tert-butyl) tellurium (Te(t-Bu)2), tert-butyl hydrotellurium (Te(t-Bu)(H)), Te(OEt)4, bis(trimethylsilyl) tellurium (Te(SiMe3)2) and bis(triethylsilyl) tellurium (Te(SiEt3)2).

[0134] This document describes other precursors and non-limiting substituents. For example, a precursor may be any having the structure of formulas (I), (II), and (IIa) as described above; or any of formulas (III), (IV), (V), (VI), (VII), or (VIII) as described below. Any of the substituents M, R, X, or L described herein may be used in formulas (I), (II), (IIa), (III), (IV), (V), (VI), (VII), or (VIII).

[0135] Non-limiting precursors include metal halides having the following formula (III): MXn (III), Where M is a metal, X is a halogen (e.g., fluorine, chlorine, bromine, or iodine), and n is 2 to 4 (depending on the choice of M). Non-limited metals of M include Sn, Te, Bi, Sb, or In. Non-limited metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0136] Another non-limiting precursor includes structures having formula (IV): MRn (IV), Wherein M is a metal; each R is independently H, an alkyl group (e.g., -NR2, where each R is independently alkyl), a (trialkylsilyl) amide group (e.g., -N(SiR3, where each R is independently alkyl), or a trialkylsilyl group (e.g., -SiR3, where each R is independently alkyl); and n is 2 to 4 (depending on the choice of M). Non-limiting metals of M include Sn, Te, Bi, Sb, or In. The alkyl group may be CnH2n+1, where n is 1, 2, 3, or greater. Non-limited organometallic agents include Sn(Me)4, Sn(Et)4, TeRn, RTeR, RTeH, tert-butyl hydrotellurium (Te(t-Bu)(H)), dimethyltellurium (TeMe2), di-tert-butyltellurium (Te(t-Bu)2), di(isopropyl)tellurium (Te(i-Pr)2), bis(trimethylsilyl)tellurium (Te(SiMe3)2), bis(triethylsilyl)tellurium (Te(SiEt3)2), tri(bis(trimethylsilyl)amino)bismuth (Bi[N(SiMe3)2]3), Sb(NMe2)3, and similar agents.

[0137] Metal-containing precursors may include covering agents having the following formula (V): MLn (V), Wherein M is a metal; each L is independently a substituted alkyl, amino (e.g., -NR1R2, where each R1 and R2 may be H or alkyl, such as any of those described herein), alkoxy (e.g., -OR, where R is alkyl, such as any of those described herein), halogen, or other organic substituent, and n is 2 to 4, depending on the choice of M. Non-limiting metals of M include Sn, Te, Bi, Sb, or In. Non-limiting coordinating groups include dialkylamino (e.g., dimethylamino, methylethylamino, and diethylamino), alkoxy (e.g., tert-butoxy and isopropoxy), halogen (e.g., F, Cl, Br, and I), or other organic substituents (e.g., acetoacetone or N2,N3-di-tert-butyl-butane-2,3-diamino). Non-limiting covering agents include SnCl4; SnI4; Sn(NR2)4, wherein each R is independently methyl or ethyl; or Sn(t-BuO)4. In some embodiments, multiple types of ligands are present.

[0138] Metal-containing precursors may include covering agents having a hydrocarbon-substituted group of the following formula (VI): Rn MXm (VI), Wherein M is a metal, R is a C2-10 alkyl or substituted alkyl group having a β-hydrogen, and X is a suitable leaving group that reacts with the hydroxyl group in the exposed hydroxyl group. In many embodiments, n = 1 to 3, and m = 4-n, 3-n, or 2-n, provided m > 0 (or m ≥ 1). For example, R can be tert-butyl, tert-pentyl, tert-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 halogens (F, Cl, Br, or I) or oxygen (-OH or -OR). X can be a dialkylamino group (e.g., dimethylamino, methylethylamino, or diethylamino), an alkoxy group (e.g., tert-butoxy, isopropoxy), a halogen (e.g., F, Cl, Br, or I), or another organic ligand. Examples of alkyl-substituted covering agents include tert-butyltris(dimethylamino)tin (Sn(t-Bu)(NMe2)3), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe2)3), tert-butyltris(diethylamino)tin (Sn(t-Bu)(NEt2)3), di(tert-butyl)di(dimethylamino)tin (Sn(t-Bu)2(NMe2)2), sec-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe2)3), n-pentyltris(dimethylamino)tin (Sn(n-pentyl)(NMe2)3), isobutyltris(dimethylamino)tin (Sn(i-Bu)(NMe2)3), and isopropyltris(dimethylamino)tin (Sn(i-Pr)(NMe2)3). ), tert-butyltris(tert-butoxy)tin (Sn(t-Bu)(t-BuO)3), n-butyltris(tert-butoxy)tin (Sn(n-Bu)(t-BuO)3) or isopropyltris(tert-butoxy)tin (Sn(i-Pr)(t-BuO)3).

[0139] In many embodiments, the metal-containing precursor includes at least one alkyl group on each metal atom that can remain in the gas-phase reaction, while other ligands or ions coordinated to the metal atom may be substituted for the reactants. Accordingly, another non-limiting metal-containing precursor includes an organometallic agent having formula (VII): Ma Rb Lc (VII), Wherein M is a metal; R is an alkyl group substituted as appropriate; L is a ligand, ion, or other moiety reactive with the relative reactant; a ≥ 1; b ≥ 1; and c ≥ 1. In a particular embodiment, a = 1, and b + c = 4. In some embodiments, M is Sn, Te, Bi, Sb, or In. In a particular embodiment, each L is independently an amino group (e.g., -NR1R2, where each R1 and R2 may be H or an alkyl group, such as any of those described herein), an alkoxy group (e.g., -OR, where R is an alkyl group, such as any of those described herein), or a halogen (e.g., F, Cl, Br, or I). Non-limiting reagents include SnMe3Cl, SnMe2Cl2, SnMeCl3, SnMe(NMe2)3, SnMe3(NMe2) and the like.

[0140] In other embodiments, the non-metallic precursor includes an organometallic agent having formula (VIII): Ma Lc (VIII), Where M is a metal; L is a ligand, ion, or other moiety reactive with the relative reactant; a ≥ 1; and c ≥ 1. In a particular embodiment, c = n-1, and n is 2, 3, or 4. In some embodiments, M is Sn, Te, Bi, Sb, or In. The relative reactant preferably has the ability to substitute the reactive moiety, ligand, or ion (e.g., L in this text) to connect at least two metal atoms through chemical bonding.

[0141] In any embodiment herein, R may be an alkyl group that is substituted as appropriate (e.g., a C1-10 alkyl group). In one embodiment, the alkyl group is substituted with one or more halogens (e.g., halogen-substituted C1-10 alkyl groups, including one, two, three, four or more halogens, such as F, Cl, Br or I). Non-limiting substituents for R include Cn H2n+1, preferably where n ≥ 3; and Cn Fx H(2n+1-x), where 1 ≤ x ≤ 2n+1 and n ≥ 1; and Cn Ix H(2n+1-x), where 1 ≤ x ≤ 2n+1 and n ≥ 1. In many embodiments, R has at least one β-hydrogen or β-fluorine or β-iodine. For example, R may be selected from the group consisting of isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, sec-pentyl and mixtures thereof.

[0142] In any embodiment herein, L may be any portion that is readily substituted by the relative reactant to produce the M-OH moiety, such as portions selected from the group consisting of amino groups (e.g., -NR1 R2, wherein each R1 and R2 may be H or alkyl, such as any of those described herein), alkoxy groups (e.g., -OR, wherein R is alkyl, such as any of those described herein), carboxyl groups, halogens (e.g., F, Cl, Br or I) and mixtures thereof.

[0143] Other non-limited organometallic agents include SnMeCl3, (N2,N3-di-tert-butyl-butane-2,3-diamino)tin(II) (Sn(tbba)), bis(bis(trimethylsilyl)amino)tin(II), tetra(dimethylamino)tin(IV) (Sn(NMe2)4), tert-butyltri(dimethylamino)tin (Sn(t-butyl)(NMe2)3), isobutyltri(dimethylamino)tin (Sn(i-Bu)(NMe2)3), n-butyltri(dimethylamino)tin (Sn(n-Bu)(NMe2)3), sec-butyltri(dimethylamino)tin (Sn(s-Bu)(NMe2)3), and isopropyl(tri)dimethylaminotin (Sn(i-Pr)(NMe2)3). ), n-propyltris(diethylamino)tin (Sn(n-Pr)(NEt2)3) and similar alkyl(tris)(tert-butoxy)tin compounds, such as tert-butyltris(tert-butoxy)tin (Sn(t-Bu)(t-BuO)3), tert-butyl hydrotelluride, di(tert-butyl)telluride, di(isopropyl)telluride or bis(trimethylsilyl)telluride. In some embodiments, the organometallic agent is partially fluorinated.

[0144] These precursors can be used alone to form EUV inhibitor materials or in combination with one or more reactive compounds. The reactive compounds preferably have the ability to substitute reactive moieties, ligands, or ions (e.g., L in this text) to chemically bond at least two metal atoms. Exemplary reactive compounds include oxygen-containing reactive compounds such as oxygen (O2), ozone (O3), water, peroxides (e.g., 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. In many embodiments, the reactive compounds react with organometallic precursors by forming oxygen bridges between adjacent metal atoms. Other potential reactive compounds include hydrogen sulfide and hydrogen disulfide, which can crosslink metal atoms through sulfur bridges; and bis(trimethylsilyl)tellurium, which can crosslink metal atoms through tellurium bridges. Additionally, hydrogen iodide can be used to bind iodine to the membrane.

[0145] Furthermore, two or more different precursors may be used within the sensitized membrane. For example, two or more of any metal-containing precursors described herein may be used, wherein one precursor includes an EUV sensitizer while the other does not. In a non-limiting example, tin telluride may be formed by using a tin precursor including an NR2 ligand and an RTeH, RTeD, or R2Te precursor, wherein R is an alkyl group, particularly tert-butyl or isopropyl. In another example, the metal telluride may be formed by using a first metal precursor containing an alkoxy or halogen ligand (e.g., SbCl3) and a telluride precursor containing a trialkylsilyl ligand (e.g., bis(trimethylsilyl)telluride).

[0146] EUV inhibitor materials or their precursors may be provided in any useful form. In one embodiment, the EUV inhibitor material or its precursor is provided in gaseous form. In a particular embodiment, the EUV inhibitor material or its precursor is provided as vapor in an inert carrier gas (e.g., H2, He, Ar, or N2). In other embodiments, the EUV inhibitor material or its precursor is provided as a gas. EUV inhibitor materials or their precursors may also be provided as plasma (e.g., the RF plasma described herein or any other plasma condition), which can be used to generate reactive species.

[0147] Other non-limiting EUV inhibitor materials, processing methods and apparatus are described in U.S. Patent No. 9,996,004; International Patent Publication No. WO 2020 / 102085; and International Patent Publication No. WO 2019 / 217749, the entire contents of each of which are incorporated herein by reference. [ Microfilm process , ] [ , ]

[0148] EUV lithography utilizes EUV resists, which can be polymer-based chemically amplified resists produced through liquid-based spin coating techniques or metal oxide-based resists produced through dry vapor deposition techniques. The lithography method may include, for example, patterning the resist to form a light pattern by exposing it to EUV radiation, and then developing the pattern by removing a portion of the resist according to the light pattern to form a mask.

[0149] It should also be understood that although this invention relates to lithography patterning techniques and materials, exemplified by EUV lithography, it can also be applied to other next-generation lithography technologies. Besides EUV, including the standard 13.5 nm EUV wavelength currently in use and under development, the most relevant radiation sources for such lithography are DUV (deep ultraviolet light), which generally refers to excimer laser sources using 248 nm or 193 nm, X-rays (which in form include EUV at lower energy ranges within the X-ray range), and electron beams (which can cover a wider energy range). These methods include contacting a substrate (e.g., optionally having exposed hydroxyl groups) with a metal-containing precursor (e.g., any of those described herein) to form a metal oxide film (e.g., a layer comprising a metal oxide bonded network, which may include other non-metallic and non-oxygen groups) as an imaging / PR layer on the substrate surface. Specific methods may depend on the particular materials and applications used in the semiconductor substrate and the final semiconductor device. Therefore, the methods described in this application are merely examples of methods and materials that can be used in this technology.

[0150] Directly photomable patternable EUV resists can be composed of or contain metals and / or metal oxides mixed within organic components. Metals / metal oxides hold promise due to their ability to enhance EUV photon absorption and generate secondary electrons, and / or to exhibit greater etch selectivity relative to the underlying film stack and device layers. To date, these resists have been developed using wet (solvent) methods, which require moving the wafer to a development track where it is exposed to a developing solvent, followed by drying and baking. Wet development not only limits productivity but also causes line collapse due to surface tension effects during solvent evaporation between small features.

[0151] Dry lithography has been proposed to overcome these problems by eliminating substrate delamination and interface cracking. Dry lithography has its own challenges, including the etching selectivity between unexposed and EUV-exposed resist materials, which may lead to a higher dose-to-size requirement for effective resist exposure compared to wet lithography. Suboptimal selectivity may also result in rounded PR corners due to prolonged exposure to etching gases, potentially increasing line CD variation in subsequent transfer etching steps. Additional processes used during lithography are detailed below. [ Deposition processes, including dry deposition , ]

[0152] As discussed above, the present invention provides a method for fabricating an imaging layer on a semiconductor substrate, which can be patterned using EUV or other next-generation lithography techniques. The method includes methods such as generating polymerized organometallic materials with vapor and depositing them onto the substrate. In some embodiments, dry deposition can employ any useful metal-containing precursor (e.g., metal halides, covering agents, or organometallic agents described herein). In other embodiments, spin-coating formulations can be used. The deposition process may include coating an EUV resist material as a resist film and / or as a sensitized film having one or more EUV sensitizers.

[0153] This technology includes a method for depositing EUV resist films on a substrate, such films being operable as resists for subsequent EUV lithography and processing. These EUV resist films include materials that change upon exposure to EUV, such as metal oxide materials that lose bulky side-group ligands bonded to metal atoms in low-density M-OH-rich materials, thereby crosslinking into more dense MOM-bonded metal oxide materials. Through EUV patterning, regions of the film with altered physical or chemical properties relative to unexposed areas are created.

[0154] These properties can be utilized in subsequent processing, such as dissolving unexposed or exposed areas, or selectively depositing material on exposed or unexposed areas. In some embodiments, under the conditions of such subsequent processing, the unexposed film has a hydrophobic surface, while the exposed film has a hydrophilic surface (it is known that the hydrophilicity of exposed and unexposed areas is relative to each other). For example, material removal can be achieved by utilizing differences in the chemical composition, density, and crosslinking of the films. Removal can be achieved by wet or dry processing, as further described herein.

[0155] The thickness of the EUV patternable film formed on the substrate surface can vary depending on the surface characteristics, the materials used, and the processing conditions. In many embodiments, the film thickness can range from about 0.5 nm to about 100 nm. Preferably, the film has a sufficient thickness to absorb most of the EUV light under EUV patterning conditions. For example, the total absorption of the resist film can be 30% or less (e.g., 10% or less, or 5% or less), allowing sufficient exposure of the resist material at the bottom of the resist film. In some embodiments, the film thickness is 10 nm to 20 nm. Without limiting the mechanism, function, or utility of the invention, it is believed that, unlike wet spin coating processes in the art, the process of the present invention has fewer limitations on the surface adhesion properties of the substrate and can therefore be applied to a variety of substrates. Furthermore, as discussed above, the deposited film can closely conform to surface features, thereby providing the advantage of forming a mask on a substrate (e.g., a substrate with underlying features) without "filling" or otherwise planarizing such features.

[0156] The film (e.g., an imaging layer) may be composed of a metal oxide layer deposited in any useful manner. These metal oxide layers may be deposited or coated using any EUV resist material described herein, such as a metal-containing precursor (e.g., a metal halide, a covering agent, or an organometallic agent). In a non-limiting process, a polymerized organometallic material is formed on a substrate surface in the gas phase or in situ to provide the metal oxide layer. The metal oxide layer may be used as a film or an adhesive layer (e.g., between the substrate and the film).

[0157] Alternatively, the metal oxide layer may include a hydroxyl-terminated metal oxide layer, which may be deposited using a covering agent (as described herein) and an oxygen-containing reactive substance. Such hydroxyl-terminated metal oxide layers may be used as an adhesive layer, for example, between two other layers, such as between a substrate and a film.

[0158] Non-limited deposition techniques (e.g., for films) include any of those described herein, such as ALD (e.g., thermal ALD and plasma-enhanced ALD), spin-coating deposition, PVD including PVD co-sputtering, CVD (e.g., PE-CVD or LP-CVD), sputtering deposition, electron beam deposition including electron beam co-evaporation, or combinations thereof, such as ALD having CVD components, such as discontinuous ALD processes containing metal precursors and relative reactants that are separated in time or space.

[0159] Generally, deposition may include mixing a vapor stream containing a metal precursor (e.g., any of those described herein, such as metal precursors, metal halides, covering agents, or organometallic agents) with a vapor stream containing a reactant, and depositing an organometallic material onto the surface of a semiconductor substrate. In some embodiments, the metal precursor and the reactant are mixed to form a polymerized organometallic material. As will be understood by those skilled in the art, the mixing and deposition aspects of the process can be performed simultaneously in a substantially continuous process.

[0160] In some embodiments, the deposition is an ALD, which is a cyclic process of depositing a metal precursor (e.g., any of those described herein, such as a metal halide, a capping agent, or an organometallic agent) and a relative reactant (e.g., an oxygen-containing relative reactant). Materials and processes that can be used to deposit metal oxide layers herein are described in Nazarov DV et al., “Atomic layer deposition of tin dioxide nanofilms: a review, 40 Rev. Adv. Mater. Sci. 262-275 (2015)”.

[0161] In a non-continuous CVD process, two or more gas streams (in separate inlet paths) containing a metal precursor (e.g., any of those described herein, such as metal halides, covering agents, or organometallic agents) and a source of a reactant are introduced into the deposition chamber of a CVD apparatus, where they mix and react in the gas phase to form a film on a substrate. These streams can be introduced, for example, using a dual-chamber spray head. The apparatus is configured to mix the metal precursor and the reactant stream in the chamber, thereby allowing the reagent to react with the reactant to form a film (e.g., a metal oxide coating or an aggregated polymer material, for example, formed through metal-oxygen-metal bonds).

[0162] To deposit metal oxides, CVD processes are typically performed under reduced pressure, for example, from 0.1 Torr to 10 Torr. In some embodiments, the process is performed at a pressure of 1 Torr to 2 Torr. The substrate temperature is preferably lower than the temperature of the reaction stream. For example, the substrate temperature can be from 0°C to 250°C, or from ambient temperature (e.g., 23°C) to 150°C.

[0163] To deposit agglomerated polymer materials, CVD processes are typically performed under reduced pressure, for example, from 10 m Torr to 10 Torr. In some embodiments, the process is performed at 0.5 to 2 Torr. The substrate temperature is preferably equal to or lower than the temperature of the reactant stream. For example, the substrate temperature can be from 0°C to 250°C, or from ambient temperature (e.g., 23°C) to 150°C. In many processes, the deposition of the polymerized organometallic material occurs at a rate inversely proportional to the surface temperature. Without limiting the mechanism, function, or practicality of this technology, it is believed that the products from these gas-phase reactions become larger in molecular weight due to the cross-linking of metal atoms with the reactants, and then the products condense or deposit on the substrate. In many embodiments, the steric barrier of large-volume alkyl groups prevents the formation of a densely packed network and produces a porous, low-density film.

[0164] A potential advantage of using dry deposition methods is the ease with which the composition of the film can be modulated during its growth. In CVD processes, this can be accomplished by altering the relative flow rates of two or more metal-containing precursors during deposition. Deposition can occur between 30°C and 200°C and at pressures between 0.01 Torr and 100 Torr, but more generally between about 0.1 Torr and 10 Torr.

[0165] Films (e.g., metal oxide coatings formed through metal-oxygen-metal bonds or aggregated polymeric materials) can also be deposited via an ALD process. For example, a metal-containing precursor and a reactant are introduced at separate intervals, representing an ALD cycle. The precursor reacts on the surface, thereby forming up to one layer of material per cycle. This allows for good control over the uniformity of film thickness across the entire surface. ALD processes are typically performed under reduced pressure, for example, from 0.1 Torr to 10 Torr. In some embodiments, the process is performed at 1 Torr to 2 Torr. The substrate temperature can be from 0°C to 250°C, or ambient temperature (e.g., 23°C) to 150°C. The process can be a thermal process, or preferably plasma-assisted deposition.

[0166] Any deposition method described herein can be modified to allow the use of two or more different metal-containing precursors. In one embodiment, the precursors may comprise the same metal but different ligands. In another embodiment, the precursors may comprise different metal groups. In a non-limiting example, alternating flows of multiple volatile metal-containing precursors can provide a mixed metal layer, for example, using a metal precursor without a sensitizer and another metal precursor having an EUV sensitizer (e.g., I).

[0167] Furthermore, any of the deposition methods described herein can be modified to provide one or more layers within the film. In one example, different precursors may be used for each layer. In another example, the same precursor may be used for each layer, but the top layer may be treated (e.g., by using plasma to remove one or more ligands within the deposited layer) to provide a different chemical composition (e.g., different densities of metal-ligand bonds).

[0168] The deposition process can be performed on any usable surface. As referred to herein, "surface" means a surface on which the film of this technology will be deposited or exposed to EUV during the process. Such surfaces may exist on a substrate (e.g., on which the film will be deposited) or on the film (e.g., on which further post-processing can be performed and on which reactions can be performed to facilitate etching in EUV-exposed or EUV-unexposed areas).

[0169] Any suitable substrate can be used, including any material configuration suitable for lithography (particularly for the production of integrated circuits and other semiconductor devices). In some embodiments, the substrate is a silicon wafer. The substrate may be a silicon wafer on which features with irregular surface morphology ("underlying morphology features") have been formed.

[0170] These underlying topographic features may include areas where material has been removed (e.g., by etching) or material has been added (e.g., by deposition) during processing prior to the present technical method. Such prior processing may include the methods of the present technique or other processing methods in an iterative process, thereby forming two or more layers of features on the substrate. Without limiting the mechanism, function, or practicality of the present technique, it is believed that in some embodiments, the methods of the present technique offer advantages over methods known in the art (which use spin casting to deposit photolithography films onto a substrate surface). These advantages may stem from the consistency of the film on the underlying features of the present technique without the need for "filling" or otherwise planarizing such features, and the ability to deposit films on a wide range of material surfaces.

[0171] In some embodiments, the substrate surface with the desired material can be used to fabricate the wafer, the topmost material of which is a layer to which a resist pattern is transferred. Although the material selection may vary depending on the level of integration, it is generally desirable to select a material that can be etched with high selectivity (i.e., much faster) than the EUV resist or imaging layer. Suitable substrate materials may include a variety of carbon-based films (e.g., ashingable hard masks (AHMs), silicon-based films (e.g., silicon, silicon oxide, silicon nitride, silicon oxynitride, or silicon oxynitride, and their doped forms, including SiOx, SiOx Ny, SiOx Cy Nz, amorphous Si:H, polycrystalline Si, or SiN), or any other (generally sacrificial) film coated to facilitate the patterning process.

[0172] In some embodiments, the substrate is a hard mask used for photolithography etching of the underlying semiconductor material. The hard mask may include any of a variety of materials, including amorphous carbon (aC), SnOx, SiO2, SiOx Ny, SiOx C, Si3N4, TiO2, TiN, W, W-doped C, WOx, HfO2, ZrO2, and Al2O3. For example, the substrate may preferably include SnOx, such as SnO2. In many embodiments, the layer may be 1 nm to 100 nm thick, or 2 nm to 10 nm thick.

[0173] In some non-limiting embodiments, the substrate includes an underlayer. The underlayer may be deposited on a hard mask or other layer and is generally beneath the imaging layer (or film), as described herein. The underlayer can be used to improve the sensitivity of the photoresist (PR), increase EUV absorption, and / or enhance the patterning performance of the PR. In examples where there are device features on the substrate to be patterned that produce significant morphologies, another important function of the underlayer can be to coat and planarize the existing morphology so that subsequent patterning steps can be performed on a flat surface with a focal pattern in all areas. For such applications, the underlayer (or at least one of the underlayers) can be coated using a spin-coating technique. When the photoresist material used has a significant inorganic component, such as exhibiting a predominantly metal oxide framework, the underlayer can advantageously be a carbon-based film, which can be coated by spin-coating or by a dry vacuum-based deposition process. The layer may include multiple ashingable mask (AHM) films having a carbon and hydrogen-based composition and may be doped with additional elements such as tungsten, boron, nitrogen, or fluorine.

[0174] In some embodiments, surface activation operations can be used to activate surfaces (e.g., the surfaces of substrates and / or films) for further processing. For example, for SiOx surfaces, water or oxygen / hydrogen plasma can be used to generate hydroxyl groups on the surface. For carbon- or hydrocarbon-based surfaces, various treatments (e.g., water, hydrogen / oxygen, or CO2 plasma, or ozone treatment) can be used to generate carboxylic acids and / or hydroxyl groups. These methods demonstrate that improving the adhesion of resist features to the substrate is crucial, as they may otherwise delaminate or peel off in solvents during processing or development.

[0175] Adhesion can also be improved by inducing roughness in the surface to increase the surface area available for interaction and by directly improving mechanical adhesion. For example, a rough surface can first be created using a sputtering process with Ar or other non-reactive ion bombardment. This surface can then be capped with the desired surface functionalities (e.g., hydroxyl and / or carboxylic acid groups) as described above. On carbon, a combined approach can be used, in which a chemically reactive oxygen-containing plasma, such as CO2, O2, H2O (or a mixture of H2 and O2), is used to etch away a thin layer of locally inhomogeneous film while capping with -OH, -OOH, or -COOH groups. This can be done with or without bias. Combining the above surface modification strategies, this method achieves the dual purpose of surface roughening and substrate surface chemical activation, for direct adhesion to inorganic metal oxide-based resists, or as an intermediate surface modification for further functionalization.

[0176] In many embodiments, the surface (e.g., the surface of a substrate and / or film) contains exposed hydroxyl groups on its surface. Generally, the surface can be any surface that contains or has been treated to create an exposed hydroxyl group surface. Such hydroxyl groups can be formed on the surface by surface treatment of the substrate using oxygen plasma, water plasma, or ozone. In other embodiments, the surface of the film can be treated to provide exposed hydroxyl groups, on which a capping layer can be coated. In many embodiments, the hydroxyl-terminated metal oxide layer has a thickness of 0.1 nm to 20 nm, or 0.2 nm to 10 nm, or 0.5 nm to 5 nm. [ EUV , ] [ Exposure of manufacturing process , ]

[0177] EUV exposure of the film can provide an EUV-exposed region with activated reaction centers including metal atoms (M) (generated through EUV-mediated cleavage events). These reaction centers may include dangling metallic bonds, MH groups, cleaved M-coordinating groups, or dimerized MM bonds. In a particular embodiment, after EUV exposure, the coordinating groups at the modified interface undergo β-hydrogen elimination, resulting in the formation of MH bonds at the interface. During this stage, or during post-exposure baking, the MH bonds may react with resists to form MOM bridges at the interface, thereby effectively improving the adhesion of the film in the exposed region.

[0178] EUV exposure in a vacuum environment can have wavelengths of about 10 nm to about 20 nm, for example, 10 nm to 15 nm, such as 13.5 nm. In particular, patterning can provide EUV exposed areas and EUV unexposed areas to form a pattern.

[0179] This technique may include patterning using EUV and DUV or electron beams. In such patterning, radiation is focused onto one or more regions of an imaging layer. Exposure is typically performed such that the imaging layer film includes one or more regions not exposed to radiation. The resulting imaging layer may include multiple exposed and unexposed areas, thereby establishing a pattern consistent with the establishment of other feature patterns of a transistor or semiconductor device, which is formed in subsequent substrate processing by adding or removing material from the substrate. EUV, DUV, and electron beam radiation methods and apparatus useful herein include methods and apparatus known in the art.

[0180] In some EUV lithography techniques, organic hard masks (e.g., ashedable hard masks of PECVD amorphous hydride carbon) are patterned using conventional photoresist processes. During photoresist exposure, EUV radiation is absorbed in the resist and the underlying substrate, generating high-energy photoelectrons (e.g., about 100 eV) followed by a series of low-energy secondary electrons (e.g., about 10 eV) that diffuse laterally over several nanometers. These electrons increase the extent of chemical reactions in the resist, enhancing its EUV dose sensitivity. However, the inherently random pattern of secondary electrons is superimposed on the optical image. This undesirable exposure of secondary electrons in the patterned resist leads to decreased resolution, significant line edge roughness (LER), and linewidth variations. These defects are replicated in the material to be patterned during subsequent pattern transfer etching.

[0181] Unlike insulating materials (e.g., photoresist), metals are less susceptible to secondary electron exposure effects because secondary electrons rapidly lose energy and heat up through scattering by conduction electrons. Suitable metal elements for this process include, but are not limited to, aluminum, silver, palladium, platinum, rhodium, ruthenium, iridium, cobalt, ruthenium, manganese, nickel, copper, hafnium, tantalum, tungsten, gallium, germanium, tin, antimony, or any combination thereof. However, electron scattering in photoresist used to pattern a blanket-coated metal film into a mask can still lead to unacceptable effects such as LER (Low Electron Reduction).

[0182] This paper discloses a vacuum-integrated metal hard mask process and related vacuum-integrated hardware that combines film formation (deposition / condensation) with optical lithography to significantly improve EUV lithography (EUVL) performance (e.g., reduce line edge roughness).

[0183] In many of the embodiments described herein, deposition (e.g., coagulation) processes (e.g., ALD or MOCVD performed in a PECVD tool such as Lam Vector®) can be used to form a thin film containing a metal, such as a photosensitive metal salt or a metal-containing organometallic compound (organometallic compound), which has strong absorption in EUV (e.g., at wavelengths in the 10 nm to 20 nm range), for example at the wavelength of an EUVL light source (e.g., 13.5 nm = 91.8 eV). This film undergoes photodecomposition after EUV exposure, forming a metal mask that serves as a pattern transfer layer during subsequent etching (e.g., in a conductor etching tool such as Lam 2300® Kiyo®).

[0184] Following deposition, the EUV-patternable thin film is patterned by exposure to an EUV beam (typically under relatively high vacuum). For EUV exposure, the metal-containing film can then be deposited in a chamber integrated with a lithography platform (e.g., a wafer stepper, such as the ASML TWINSCAN NXE: 3300B® platform in Veldhoven, Netherlands), and transferred under vacuum to prevent reaction before exposure. Integration with lithography tools is driven by the strong light absorption of incident photons by ambient gases (e.g., H₂O, O₂, etc.) and the significant pressure reduction required for EUVL. In other embodiments, photosensitive metal film deposition and EUV exposure can be performed in the same chamber. [ Development process, including dry development , ]

[0185] Any useful developing process can be used to remove EUV-exposed areas or EUV-unexposed areas. In one embodiment, the EUV-exposed areas may have MH groups, which can be selectively removed by employing one or more dry developing processes (e.g., halide chemistry). In another embodiment, the EUV-exposed areas may be further crosslinked, while the EUV-unexposed areas can be selectively removed by employing one or more dry developing processes (e.g., halide chemistry).

[0186] Dry development processes may include the use of halides, such as HCl or HBr-based processes. While the invention is not limited to any particular theory or operating mechanism, the method is understood to utilize the chemical reactivity of dry-deposited EUV photoresist films with cleaning chemicals (e.g., HCl, HBr, and BCl3) using steam or plasma to form volatile products. Dry-deposited EUV photoresist films can be removed at etching rates up to 1 nm / s. Rapid removal of dry-deposited EUV photoresist films using these chemical methods can be used for chamber cleaning, backside cleaning, bevel cleaning, and PR development. While steam at various temperatures (e.g., HCl or HBr above -10°C, or BCl3 above 80°C) can be used to remove the film, plasma can also be used to further accelerate or enhance reactivity.

[0187] Plasma processes include transformer-coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP) processes using equipment and technologies known in the art. For example, the process can be performed at a pressure of >5 mTorr (e.g., >15 mTorr, such as 20 mTorr to 100 mTorr) and a power level of <1000 W (e.g., <500 W). Temperatures can range from 30°C to 300°C (e.g., 30°C to 120°C), flow rates from 100 to 1000 standard cubic centimeters per minute (sccm), for example, approximately 500 sccm, for durations from 1 to 3000 seconds (e.g., 10 seconds to 600 seconds).

[0188] With the halide reactant stream consisting of hydrogen and halide gases, remote plasma / UV radiation is used to generate free radicals from H2, Cl2, and / or Br2. The hydrogen and halide free radicals flow into the reaction chamber to contact the patterned EUV photoresist on the wafer's substrate layer. Suitable plasma power ranges from 100 W to 500 W without bias. It should be understood that while these conditions are applicable to some processing reactors, such as the Kiyo etching tools available from Lam Research Corporation in Fremont, California, a wide range of process conditions can be used depending on the capabilities of the processing reactor.

[0189] In a thermal development process, the substrate is exposed to dry developing chemicals (e.g., Lewis acids) in a vacuum chamber (e.g., an oven). A suitable chamber may include a vacuum line, a dry developing hydrogen halide chemical gas line (e.g., HBr, HCl), and a heater for temperature control. In some embodiments, the interior of the chamber may be coated with an anti-corrosion film, such as an organic polymer or inorganic coating. Such coatings are polytetrafluoroethylene (PTFE), for example, Teflon 1M. These materials can be used in the thermal process of this invention without the risk of removal by plasma exposure.

[0190] The process conditions for dry development can be 100 sccm to 500 sccm reactant flow rate (e.g., 500 sccm HBr or HCl), -10°C to 120°C (e.g., -10°C), 20 mTorr to 500 mTorr (e.g., 300 mTorr) pressure, plasma-free, and for a duration of about 10 seconds to 1 minute, depending on the photoresist film and its composition and properties.

[0191] In many embodiments, the method of the present invention combines all the dry steps of film formation via vapor deposition, (EUV) photolithography patterning, and dry development. In these processes, after photolithography in an EUV scanner, the substrate can directly enter the dry development / etching chamber. These processes avoid the material and production costs associated with wet development. Dry processes also provide greater adjustability and allow for further CD control and / or scum removal.

[0192] In many embodiments, EUV photoresist (containing a content of some metals, metal oxides, and organic components) can be dry-developed by a combination of thermal, plasma (e.g., possibly including photoactivated plasma, such as lamp heating or UV lamp heating), or thermal and plasma methods, and by flowing a dry developing gas containing a compound of the formula RxZy (where R = B, Al, Si, C, S, SO, x > 0, and Z = Cl, H, Br, F, CH4, and y > 0). Dry development can produce a positive type, wherein the RxZy species selectively remove the exposed material, leaving the unexposed corresponding portion as a mask. In some embodiments, the exposed portion of the organotin oxide-based photoresist film is removed by dry development according to the present invention. Positive dry development can be achieved through selective dry development (removal) of EUV-exposed areas, which are exposed to a stream containing hydrogen halides or hydrogen and halides (including HCl and / or HBr) without impacting the plasma, or a stream containing H2 and Cl2 and / or Br2, and have remote plasma or UV radiation generated by plasma to generate free radicals. [ Post-coating process , ] [ , ]

[0193] The methods described herein may include any useful post-coating processes, as described below.

[0194] For backside and bevel cleaning processes, vapor and / or plasma can be confined to specific areas of the wafer to ensure that only the backside and bevel are removed, while no film degradation occurs on the front side of the wafer. The removed dry-deposited EUV photoresist film is generally composed of Sn, O, and C, but the same cleaning method can be extended to films of other metal oxide resists and materials. Furthermore, this method can also be used for film stripping and PR rework.

[0195] Suitable process conditions for dry bevel and backside cleaning include reactant flow rates of 100 sccm to 500 sccm (e.g., 500 sccm HCl, HBr, or H2 with Cl2 or Br2, BCl3, or H2), temperatures of -10°C to 120°C (e.g., 20°C), pressures of 20 mTorr to 500 mTorr (e.g., 300 mTorr), plasma power of 0 to 500 W at high frequencies (e.g., 13.56 MHz), and durations of approximately 10 to 20 seconds, depending on the photoresist film and its composition and properties. It should be understood that while these conditions are suitable for some processing reactors, such as the Kiyo etching tools available from Lam Research Corporation in Fremont, California, a wide range of process conditions can be used depending on the capabilities of the processing reactor.

[0196] Lithography processes typically include one or more baking steps to facilitate the chemical reactions required to create chemical contrast between the exposed and unexposed areas of the photoresist. For high-volume manufacturing (HVM), these baking steps are usually performed on a developing machine, where the wafers are baked in ambient air or, in some cases, under a nitrogen stream on a hot plate at a preset temperature. During these baking steps, more careful control of the baking environment and the introduction of additional reactive gas components into the environment can help further reduce dosage requirements and / or improve pattern fidelity.

[0197] According to various embodiments of the present invention, one or more post-treatments (after deposition, e.g., post-coating bake (PAB); and / or after exposure, e.g., post-exposure bake (PEB); and / or after development, e.g., post-development bake (PDB)) of metal- and / or metal oxide-based photoresists can improve the material property differences between exposed and unexposed photoresists, thereby reducing dose-to-size (DtS), improving PR profiles, and improving line edge and width roughness (LER / LWR) after subsequent dry development. These treatments may involve heat treatment with controlled temperature, gas environment, and moisture, thereby improving the performance of dry development in subsequent processing. In some instances, remote plasma may be used.

[0198] In post-coating treatments (e.g., PAB), a thermal process can be used after deposition and before exposure to modify the composition of the unexposed metal and / or metal oxide photoresist by controlling the temperature, gas environment (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, N2O, NO, Ar, He, or mixtures thereof), or under vacuum, and with moisture. This modification can increase the material's EUV sensitivity and thus achieve a lower dose ratio for size and edge roughness after exposure and dry development.

[0199] In post-exposure processing (e.g., PEB), the composition of both the unexposed and exposed photoresist can be altered by controlling the temperature, gas environment (e.g., air, H₂O, CO₂, CO, O₂, O₃, CH₄, CH₃OH, N₂, H₂, NH₃, N₂O, NO, Ar, He, or mixtures thereof), or by using a thermal process under vacuum and moisture. This alteration can increase the difference in composition / material properties between the unexposed and exposed photoresist, as well as the difference in etching rates of the dry development etching gases between them. This results in higher etching selectivity. Due to improved selectivity, a square PR profile with improved surface roughness and / or less photoresist residue / dross can be obtained.

[0200] In examples of post-development processing (e.g., post-development baking or PDB), the composition of the unexposed photoresist can be altered by controlling the temperature, gas environment (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, N2O, NO, Ar, He, or mixtures thereof) or under vacuum (e.g., with UV), and moisture in a thermal process. In certain embodiments, these conditions also include the use of plasma (e.g., comprising O2, O3, Ar, He, or mixtures thereof). This alteration can enhance the hardness of the material, which may be advantageous if the film is used as a resist mask during etching of the underlying substrate.

[0201] In these examples, in alternative implementations, the thermal process can be replaced by a remote plasma process to increase reactive species, thereby reducing the energy barrier to the reaction and increasing productivity. Remote plasma can generate more reactive free radicals, thus reducing the reaction temperature / time used for processing, thereby increasing productivity.

[0202] Accordingly, one or more processes can be applied to modify the photoresist itself to increase the selectivity of dry development. This thermal or radical modification increases the contrast between the unexposed and exposed materials, thus increasing the selectivity of subsequent dry development steps. The resulting difference in material properties between the unexposed and exposed materials can be modulated by adjusting process conditions (including temperature, gas flow rate, moisture, pressure, and / or RF power). The greater process freedom achievable with dry development (not limited by the solubility of materials in wet developers) allows for the application of more stringent conditions to further enhance the achievable material contrast. The resulting high material contrast allows for a wider process window in dry development, thus achieving higher productivity, lower costs, and better defect performance.

[0203] The main limitation of wet-developed resist films is the restricted baking temperature. Since wet development depends on material solubility, heating to, for example, 220°C or higher significantly increases the cross-linking degree between the exposed and unexposed areas of the metal-containing resist film, making both insoluble in the wet-developing solvent. Thus, the film can no longer be reliably wet-developed. For dry-developed resist films (where only the exposed or unexposed portions of the resist are removed due to the difference in etching rates (i.e., selectivity) between the exposed and unexposed areas of the resist), the processing temperature in PAB, PEB, or PDB can vary within a much wider window to modulate and optimize the processing, for example, approximately 90°C to 250°C (e.g., 90°C to 190°C) for PAB, and approximately 170°C to 250°C or higher (e.g., 190°C to 240°C) for PEB and / or PDB. Lower etching rates and greater etching selectivity have been found to occur at higher processing temperatures within the aforementioned range.

[0204] In certain embodiments, PAB, PEB, and / or PDB treatments can be performed at a gas flow rate ranging from 100 sccm to 10,000 sccm, a moisture content ranging from a few percent to 100% (e.g., 20%-50%), a pressure between atmospheric pressure and vacuum, and a duration of about 1 to 15 minutes (e.g., about 2 minutes).

[0205] These findings can be used to modulate processing conditions to tailor or optimize processing for specific materials and situations. For example, for a given EUV dose, the selectivity achievable with a PEB heat treatment at 220°C to 250°C for about 2 minutes in air with approximately 20% humidity can be similar to that of an EUV dose approximately 30% higher without such heat treatment. Therefore, depending on the selectivity requirements / constraints of the semiconductor processing operation, heat treatments such as those described herein can be used to reduce the required EUV dose. Alternatively, if higher selectivity is required and a higher dose is permissible, much higher selectivity than that achievable under wet development conditions can be obtained, with an exposure ratio up to 100 times higher than unexposed. [ equipment , ] [ , ]

[0206] This invention also includes any device configured to perform any of the methods described herein. In one embodiment, the device for depositing a sensitized film includes a deposition module comprising a chamber for depositing EUV resist material and / or EUV sensitizer into a film; a patterning module comprising an EUV lithography tool having a radiation source with a wavelength of less than 30 nm; and a developing module comprising a chamber for developing the film.

[0207] The device 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 programmed to execute film deposition instructions. These instructions may include, in a deposition module, depositing a sensitized film on the top surface of a substrate; in a patterning module, directly patterning the film through EUV exposure at a resolution of less than 30 nm, thereby forming a pattern within the film; and in a developing module, developing the film. In a particular embodiment, the developing module is provided for removing EUV-exposed or EUV-unexposed areas, thereby providing a pattern within the film.

[0208] Figure 3 illustrates a schematic diagram of an embodiment of a process station 300 having a process chamber body 302 that maintains a low-pressure environment, suitable for implementing the dry stripping and developing embodiments. Multiple process stations 300 may be contained within a common low-pressure process tool environment. For example, Figure 4 illustrates an embodiment of a multi-station processing tool 400, such as the VECTOR® processing tool available from Lam Research Corporation in Fremont, California. In some embodiments, one or more hardware parameters of the process station 300 (including those discussed in detail below) may be programmed by one or more computer controllers 350.

[0209] Process stations can be configured as modules within a cluster of tools. Figure 6 illustrates a semiconductor process cluster tool architecture with vacuum-integrated deposition and patterning modules suitable for implementing the embodiments described herein. Such cluster process tool architectures may include resist deposition, resist exposure (EUV scanner), resist dry development, and etching modules, as described herein with reference to Figures 5 and 6.

[0210] In some embodiments, certain processing functions can be performed continuously in the same module, such as dry development and etching. Furthermore, embodiments of the present invention relate to methods and apparatus for: receiving a wafer (including a photopatterned EUV resist film layer disposed on a layer or stack to be etched) into a dry development / etching chamber after photopatterning in an EUV scanner; performing dry development on the photopatterned EUV resist film layer; and subsequently etching an underlying layer using the patterned EUV resist as a mask, as described herein.

[0211] Referring back to Figure 3, process station 300 is in fluid communication with reactant delivery system 301a to deliver process gases to distribution spray heads 306 via connection 305. Reactant delivery system 301a optionally includes mixing container 304 for mixing and / or regulating process gases for delivery to spray heads 306. One or more mixing container inlet valves 320 control the introduction of process gases into mixing container 304. Under plasma exposure, plasma can also be delivered to spray heads 306, or it can be generated within process station 300.

[0212] Figure 3 includes an optional vaporization point 303 for vaporizing liquid reactants to be supplied to mixing vessel 304. In some embodiments, a liquid flow controller (LFC) may be provided upstream of vaporization point 303 to control the mass flow rate of the liquid for vaporization and delivery to process station 300. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. The plunger valve of the LFC may then be adjusted in response to feedback control signals provided by a proportional-integral-derivative (PID) controller electrically connected to the MFM.

[0213] The spray head 306 distributes process gases to the substrate 312. In the embodiment shown in FIG3, the substrate 312 is located below the spray head 306 and is shown resting on the base 308. The spray head 306 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to the substrate 312.

[0214] In some embodiments, the base 308 may be raised or lowered to expose the substrate 312 in the volume between the substrate 312 and the spray head 306. It will be appreciated that in some embodiments, the base height may be adjusted in a programmed manner via a suitable computer controller 350.

[0215] In some embodiments, the base 308 may be temperature-controlled via a heater 310. In some embodiments, during plasmaless thermal exposure of the photopatterning resist to dry developing chemicals (e.g., HBr, HCl, or BCl3), the base 308 may be heated to above 0°C and up to 300°C or higher, for example 50 to 120°C, such as about 65 to 80°C, as described in the disclosed embodiments.

[0216] Furthermore, in some embodiments, pressure control of process station 300 can be provided via butterfly valve 318. As shown in the embodiment of FIG3, butterfly valve 318 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of process station 300 can also be adjusted by changing the flow rate of one or more gases introduced into process station 300.

[0217] In some embodiments, the position of the spray head 306 can be adjusted relative to the base 308 to change the volume between the substrate 312 and the spray head 306. Furthermore, it will be understood that the vertical position of the base 308 and / or the spray head 306 can be varied within the scope of the invention by any suitable mechanism. In some embodiments, the base 308 may include a rotation axis for rotating the orientation of the substrate 312. It will be understood that in some embodiments, one or more of these exemplary adjustments can be performed in a programmed manner by one or more suitable computer controllers 350.

[0218] In plasma-enabled environments (e.g., in mild plasma-based deposition embodiments and / or etching operations within the same chamber), the spray head 306 and base 308 are electrically communicated with the radio frequency (RF) power supply 314 and matching network 316 to power the plasma 307. In some embodiments, the plasma energy can be controlled by controlling one or more of the following: process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power supply 314 and matching network 316 can operate at any suitable power to form a plasma with the desired free radical species composition. Examples of suitable power are up to about 500 W.

[0219] In some embodiments, instructions for controller 350 may be provided via input / output control (IOC) sequence instructions. In one example, instructions for setting conditions for a process stage may be included in the corresponding recipe stage of the process recipe. In some embodiments, process recipe stages may be sequentially arranged such that all instructions for a process stage are executed simultaneously with that process stage. In some embodiments, instructions for setting one or more reactor parameters may be included in the recipe stage. For example, the recipe stage may include instructions for setting the flow rate of a dry developing chemical reaction gas (e.g., HBr or HCl) and instructions for a time delay in the recipe stage. In some embodiments, controller 350 may include any of the features described below with respect to system controller 450 of FIG4.

[0220] As described above, one or more process stations may be included in a multi-station processing tool. Figure 4 shows a schematic diagram of an embodiment of a multi-station processing tool 400 having an inbound loading chamber 402 and an outbound loading chamber 404 (one or both of which may include a remote plasma source). A robot 406, operating at atmospheric pressure, is configured to move a wafer from a pod loaded through a transfer pod 408 to the inbound loading chamber 402 via an atmospheric port 410. The wafer is placed on a base 412 in the inbound loading chamber 402 by the robot 406, the atmospheric port 410 is closed, and then the loading chamber is pumped out. In the case where the inbound loading chamber 402 includes a remote plasma source, the wafer may be exposed to remote plasma processing before being introduced into the processing chamber 414 to process the silicon nitride surface in the loading chamber. In addition, the wafer may also be heated in the inbound loading chamber 402, for example, to remove moisture and adsorbed gases. Next, the chamber transfer port 416 to the processing chamber 414 is opened, and another robot (not shown) places the wafer onto the base of the first station in the reactor (shown in the reactor) for processing. Although the embodiment shown in Figure 4 includes a loading chamber, it will be understood that in some embodiments, the wafer may be provided directly into the process station.

[0221] The illustrated processing chamber 414 includes four process stations, numbered 1 to 4 in the embodiment shown in FIG. 4. Each station has a heating base (shown as 418 of station 1) and a gas line inlet. It will be understood that in some embodiments, each process station may have different or multiple purposes. For example, in some embodiments, the process station may switch between dry developing and etching process modules. Additionally or alternatively, in some embodiments, processing chamber 414 may include one or more pairs of matched dry developing and etching process stations. Although the illustrated processing chamber 414 includes four stations, it will be understood that the processing chamber according to the invention 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.

[0222] Figure 4 illustrates an embodiment of a wafer handling system 490 for transferring wafers within a processing chamber 414. In some embodiments, the wafer handling system 490 can transfer wafers between multiple process stations and / or between process stations and loading chambers. It will be appreciated that any suitable wafer handling system can be employed. Non-limiting examples include wafer conveyors and wafer handling robots. Figure 4 also illustrates an embodiment of a system controller 450 for controlling process conditions and the hardware state of process tooling 400. The system controller 450 may include one or more memory devices 456, one or more mass storage devices 454, and one or more processors 452. The processor 452 may include a central processing unit (CPU) or computer, analog and / or digital input / output connections, a stepper motor controller board, etc.

[0223] In some embodiments, system controller 450 controls all activities of process tool 400. System controller 450 executes system control software 458 stored in mass storage device 454, loaded into memory device 456, and executed on processor 452. Alternatively, control logic can be hard-coded into controller 450. Application-specific integrated circuits, programmable logic devices (e.g., field-programmable gate arrays or FPGAs) and the like can be used for these purposes. In the following discussion, regardless of whether "software" or "coding" is used, functionally equivalent hard-coded logic can be used in this situation. System control software 458 may include parameters for controlling timing, gas mixing, gas flow rate, chamber and / or station pressure, chamber and / or station temperature, wafer temperature, target power level, RF power level, substrate base, chuck and / or die position, and other parameters for specific processes executed by process tool 400. System control software 458 can be configured in any suitable manner. For example, numerous process tool component subroutines or control objects can be written to control the operation of the process tool components used to implement the various process tool processes. The system control software 458 can be coded in any suitable computer-readable programming language.

[0224] In some embodiments, system control software 458 may include input / output control (IOC) sequence instructions for controlling the aforementioned parameters. In some embodiments, other computer software and / or programs stored on a mass storage device 454 and / or memory device 456 associated with system controller 450 may be used. Examples of programs or program fragments used for this purpose include substrate positioning programs, process gas control programs, pressure control programs, heater control programs, and plasma control programs.

[0225] The substrate positioning program may include program code for a process tool assembly used to load the substrate onto the base 418 and control the spacing between the substrate and other components of the process tool 400.

[0226] The process gas control program may include codes for controlling various gas components (e.g., HBr or HCl gases as described herein) and flow rates; and optionally for allowing gas to flow into one or more process chambers prior to deposition to stabilize the pressure within the process chambers. The pressure control program may include codes for controlling the pressure within the process station by adjusting, for example, throttle valves in the process station's exhaust system, the gas flow rate entering the process station, etc.

[0227] The heater control program may include coding to control the current flowing to the heating unit used to heat the substrate. Alternatively, the heater control program may control the delivery of a heat-conducting gas (e.g., helium) to the substrate.

[0228] The plasma control program may include coding for setting the RF power level applied to process electrodes in one or more process stations, according to embodiments herein.

[0229] The pressure control program may include coding for maintaining the pressure within the reaction chamber, according to the embodiments herein.

[0230] In some embodiments, a user interface may be associated with the system controller 550. The user interface may include a display screen, a graphical software display of device and / or process conditions, and a user input device (e.g., a pointing device, a keyboard, a touch screen, a microphone, etc.).

[0231] In some embodiments, the parameters adjusted by the system controller 450 may be related to process conditions. Non-limiting examples include process gas composition and flow rate, temperature, pressure, plasma conditions (e.g., RF bias power level), etc. These parameters may be provided to the user in the form of a recipe (which can be input via a user interface).

[0232] Signals for monitoring the process can be obtained from various process tool sensors via the analog and / or digital input connectors of the system controller 450. Signals for controlling the process can be output on the analog and / or digital output connectors of the process tool 400. Non-limiting examples of process tool sensors that can be monitored include mass flow controllers, pressure sensors (e.g., pressure gauges), thermocouples, etc. Appropriately programmed feedback and control algorithms can be used with data from these sensors to maintain process conditions.

[0233] The system controller 450 provides programming instructions for implementing the deposition process described above. These programming instructions can control various process parameters, such as DC power level, RF bias power level, pressure, temperature, etc. These instructions can control these parameters to operate dry development and / or etching processes according to the various embodiments described herein.

[0234] System controller 450 will typically include one or more memory devices and one or more processors configured to execute the instructions such that the device will perform the method according to the disclosed embodiments. Machine-readable media (containing instructions for controlling process operations according to the disclosed embodiments) may be coupled to system controller 450.

[0235] In some embodiments, the system controller 450 is part of a system, which may be part of one of the examples described above. Such systems may include semiconductor processing equipment comprising a processing tool or multiple tools, a chamber or multiple chambers, a processing platform or multiple platforms, and / or specific processing components (wafer pedestals, airflow systems, etc.). Such systems may be combined with electronic equipment to control the operation of semiconductor wafers or substrates before, during, and after processing. Such electronic equipment may refer to a "controller" that controls various components or sub-components of the system or multiple systems. Depending on the processing conditions and / or system type, the system controller 450 may be programmable to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, and wafer transfer (entry and exit from tools and other transfer tools connected or coupled to a specific system, and / or loading chambers).

[0236] Broadly speaking, system controller 450 can be defined as an electronic device having various integrated circuits, logic, memory, and / or software for receiving instructions, issuing instructions, controlling operations, initiating cleaning operations, initiating endpoint measurements, and the like. Integrated circuits may include: a chip in the form of firmware storing program instructions, a digital signal processor (DSP), a chip defined as an application-specific integrated circuit (ASIC), and / or one or more microprocessors, or a microcontroller executing program instructions (e.g., software). Program instructions may be instructions transmitted to system controller 450 in the form of various individual settings (or program files), which define operating parameters for implementing a specific process (on a semiconductor wafer, or for a semiconductor wafer, or for a system). In some embodiments, the operating parameters may be part of a formulation defined by a process engineer to achieve one or more processing steps during the manufacturing process of one or more of the following: layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer grains.

[0237] In some embodiments, the system controller 450 may be part of a computer, or coupled to a computer that is integrated with, coupled to, or connected to the system via other networks, or a combination thereof. For example, the system controller 450 may be in all or part of a cloud-based or factory mainframe computer system that allows remote access to wafer processing. The computer enables the system to remotely access and monitor the current progress of manufacturing operations, examine the history of past manufacturing operations, check trends or performance metrics from multiple manufacturing operations, change parameters for the current process, set processing steps after the current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system via a network, which may include a local area network or the Internet. The remote computer may include a user interface capable of parameter and / or setting input or programming, which can then be transmitted from the remote computer to the system. In some examples, system controller 450 receives instructions in the form of data that specify parameters for each processing step to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool with which system controller 450 is coupled or controlled. Therefore, as described above, system controller 450 may be distributed, for example, by comprising one or more separate controllers networked together and operating toward a common purpose (e.g., the processes and control described herein). An example of a distributed controller for this purpose is one or more integrated circuits on the chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer), both combined to control the process on the chamber.

[0238] Exemplary systems may include, but are not limited to, plasma etching chambers or modules, deposition chambers or modules, rotary cleaning chambers or modules, metal plating chambers or modules, cleaning chambers or modules, bevel edge etching chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, atomic layer deposition (ALD) chambers or modules, atomic layer etching (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, EUV lithography chambers (scanners) or modules, dry developing chambers or modules, and any other semiconductor processing systems that may be associated with or used in the manufacture and / or processing of semiconductor wafers.

[0239] As described above, depending on the process steps or plural steps to be performed with recourse to the tool, the system controller 450 may communicate with one or more of the following in a semiconductor manufacturing plant: other tool circuits or modules, other tooling components, cluster tools, other tool interfaces, adjacent tools, adjacent tools, tools distributed throughout the plant, a master computer, another controller, or tools used in the material transport to and from the ports used in the material transport / carriage ports.

[0240] An inductively coupled plasma (ICP) reactor, which in certain embodiments may be applicable to etching operations suitable for implementing certain embodiments, is now described. Despite the description of ICP reactors herein, in some embodiments, it should be understood that capacitively coupled plasma reactors can also be used.

[0241] 5 schematically illustrates a cross-sectional view of an inductively coupled plasma equipment 500 suitable for implementing certain embodiments or embodiments such as dry development and / or etching, exemplified by a Kiyo® reactor produced by Lam Research Corporation, Ferrimon Collin, California. In other embodiments, other tools or tool types having the function of performing the dry development and / or etching processes described herein may be used for implementation.

[0242] The inductively coupled plasma equipment 500 includes the entire process chamber structurally defined by the chamber wall 501 and window 511 . The chamber wall 501 may be made of stainless steel or aluminum. Window 511 may be made of quartz or other dielectric material. The optional internal plasma grille 550 divides the entire process chamber into an upper secondary chamber 502 and a lower secondary chamber 503 . In most embodiments, the plasma grille 550 may be removed, thereby utilizing the chamber space constituted by the sub-chambers 502 and 503 . The suction cup 517 is located within the lower sub-chamber 503 near the bottom inner surface. The suction cup 517 is configured to receive and hold a semiconductor wafer 519 on which the etching and deposition process is performed. The suction cup 517 may be an electrostatic suction cup used to support the wafer 519 (when present). In some embodiments, the edge ring (not shown) surrounds the suction cup 517 and has an upper surface that is substantially flat with the top surface of the wafer 519 (when present above the suction cup 517). Suction cup 517 also includes an electrostatic electrode for adsorption and desorption of wafer 519 . For this purpose, a filter and direct current (DV) bit power supply source (not shown) can be provided.

[0243] Other control systems may also be provided for lifting the wafer 519 away from the chuck 517. The chuck 517 can be charged using an RF power supply 523. The RF power supply 523 is connected to a matching circuit 521 via a connection 527. The matching circuit 521 is connected to the chuck 517 via a connection 525. In this manner, the RF power supply 523 is connected to the chuck 517. In many embodiments, depending on the process performed according to the disclosed embodiments, the bias power of the electrostatic chuck may be set to approximately 50 V or may be set to a different bias power. For example, the bias power may be between approximately 20 Vb and approximately 100 V, or between approximately 30 V and approximately 150 V.

[0244] The element for generating plasma includes a coil 533 located above window 511. In some embodiments, the disclosed embodiment does not use a coil. The coil 533 is made of a conductive material and includes at least one full turn. The example coil 533 shown in FIG5 includes three turns. The cross-section of the coil 533 is shown in symbols, with the coil having an "X" extending into the page and the coil having a "●" extending out of the page. The element for generating plasma also includes an RF power supply 541 configured to supply RF power to the coil 533. Generally, the RF power supply 541 is connected to a matching circuit 539 via connection 545. The matching circuit 539 is connected to the coil 533 via connection 543. In this way, the RF power supply 541 is connected to the coil 533. An optional Faraday shield 549 is located between the coil 533 and window 511. The Faraday shield 549 may be spaced apart relative to the coil 533. In some embodiments, the Faraday shield 549 is positioned directly above window 511. In some embodiments, the Faraday shield 549 is located between the window 511 and the suction cup 517. In some embodiments, the Faraday shield 549 is not spaced apart from the coil 533. For example, the Faraday shield may be directly below the window without gaps. The coil 533, the Faraday shield 549, and the window 511 are each configured to be substantially parallel to each other. The Faraday shield 549 prevents metal or other species from depositing on the window 511 of the process chamber.

[0245] Process gases can flow into the process chamber through one or more main gas inlets 560 located in the upper secondary chamber 502 and / or through one or more side gas inlets 570. Similarly, although not explicitly shown, similar gas inlets can be used to supply process gases to the capacitively coupled plasma processing chamber. A vacuum pump (e.g., a first- or second-order mechanical dry and / or turbomolecular pump) 540 can be used to extract process gases from the process chamber and maintain pressure within the process chamber. For example, during the flushing operation of the ALD, the vacuum pump can be used to evacuate the lower secondary chamber 503. Valve-controlled conduits can be used to fluidly connect the vacuum pump to the process chamber to selectively control the application of the vacuum environment provided by the vacuum pump. This can be accomplished using a closed-loop controlled flow-limiting device during plasma processing, such as a throttle valve (not shown) or a pendulum (not shown). Similarly, a vacuum pump and valve-controlled fluid connection can also be used for the capacitively coupled plasma processing chamber.

[0246] During operation of the apparatus 500, one or more process gases may be supplied through airflow inlets 560 and / or 570. In some embodiments, process gases may be supplied only through the main airflow inlet 560 or only through the side airflow inlet 570. In some examples, the airflow inlets shown in the figure may be replaced by more complex airflow inlets (e.g., one or more spray heads). The Faraday shield 549 and / or optional grille 550 may include internal channels and orifices that allow process gases to be delivered to the process chamber. One or both of the Faraday shield 549 and optional grille 550 may serve as spray heads for the delivery of process gases. In some embodiments, a liquid vaporization and delivery system may be located upstream of the process chamber, such that once the liquid reactant or precursor is vaporized, the vaporized reactant or precursor is introduced into the process chamber through airflow inlets 560 and / or 570.

[0247] Radio frequency (RF) power is supplied from RF power source 541 to coil 533, causing RF current to flow through coil 533. The RF current flowing through coil 533 generates an electromagnetic field around coil 533. The electromagnetic field induces a current in the upper secondary chamber 502. Numerous generated ions and free radicals interact physically and chemically with wafer 519 to etch feature areas of wafer 519 and selectively deposit layers on wafer 519.

[0248] If a plasma grid 550 is used, resulting in both an upper sub-chamber 502 and a lower sub-chamber 503, an induced current acts on the gas present in the upper sub-chamber 502 to generate an electron-ion plasma in the upper sub-chamber 502. The optional internal plasma grid 550 limits the number of thermionic electrons in the lower sub-chamber 503. In some embodiments, the device 500 is designed and operated such that the plasma present in the lower sub-chamber 503 is an ion-ion plasma.

[0249] Both the upper electron-ion plasma and the lower ion-ion plasma can contain both positive and negative ions, but the ion-ion plasma will have a greater ratio of negative to positive ions. Volatile etching and / or deposition byproducts can be removed from the lower sub-chamber 503 through port 522. The chuck 517 disclosed herein can operate at elevated temperatures between approximately 10°C and approximately 250°C. The temperature will depend on the process operation and specific formulation.

[0250] When the device 500 is installed in a cleanroom or manufacturing facility, it can be coupled to the facility (not shown). The facility includes piping for providing process gases, vacuum, temperature control, and environmental particle control. When installed in a target manufacturing facility, these facilities are coupled to the device 500. Additionally, the device 500 can be coupled to a transfer chamber, which allows robots to use typical automation to transfer semiconductor wafers in and out of the device 500.

[0251] In some embodiments, system controller 530 (which may include one or more physical or logic controllers) controls some or all of the operations of the process chambers. System controller 530 may include one or more memory devices and one or more processors. In some embodiments, device 500 includes a switching system for controlling flow rate and duration when performing the disclosed embodiments. In some embodiments, device 500 may have a switching time of up to about 600 ms or up to about 750 ms. Switching time may depend on flow chemistry, selected formulation, reactor structure, and other factors.

[0252] In some embodiments, the system controller 530 is part of a system, which may be part of one of the examples described above. Such systems may include semiconductor processing equipment comprising a processing tool or multiple tools, a chamber or multiple chambers, a processing platform or multiple platforms, and / or specific processing components (wafer pedestals, airflow systems, etc.). Such systems may be combined with electronic equipment to control the operation of semiconductor wafers or substrates before, during, and after processing. Such electronic equipment may be integrated into the system controller 530, which can control various components or sub-components of the system or multiple systems. Depending on the processing conditions and / or system type, the system controller may be programmable to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, and wafer transfer (entry and exit from tools and other transfer tools connected or coupled to a specific system, and / or loading chambers).

[0253] Broadly speaking, the system controller 530 can be defined as an electronic device having various integrated circuits, logic, memory, and / or software for receiving instructions, issuing instructions, controlling operations, initiating cleaning operations, initiating endpoint measurements, and the like. Integrated circuits may include: a chip in the form of firmware storing program instructions, a digital signal processor (DSP), a chip defined as an application-specific integrated circuit (ASIC), and / or one or more microprocessors, or a microcontroller executing program instructions (e.g., software). Program instructions may be instructions transmitted to the controller in the form of various individual settings (or program files) that define operating parameters for a specific process (on a semiconductor wafer, or for a semiconductor wafer, or for a system). In some embodiments, the operating parameters may be part of a formulation defined by a process engineer to achieve one or more processing steps during the manufacturing process of one or more of the following: layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer grains.

[0254] In some embodiments, the system controller 530 may be part of a computer, or coupled to a computer that is integrated with, coupled to, or networked with the system, or a combination thereof. For example, the controller may be located in all or part of a cloud-based or factory mainframe computer system that allows remote access to wafer processing. The computer enables the system to remotely access and monitor the current progress of manufacturing operations, examine the history of past manufacturing operations, check trends or performance metrics from multiple manufacturing operations, change parameters for the current process, set processing steps after the current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system via a network, which may include a local area network or the Internet. The remote computer may include a user interface capable of parameter and / or setting input or programming, which can then be transmitted from the remote computer to the system. In some examples, the system controller 530 receives instructions in the form of data specifying parameters for each processing step to be performed during one or more operations. It should be understood that parameters can be specific to the type of process to be performed and the type of tool with which the controller is coupled or controlled. Therefore, as described above, the system controller 530 can be distributed, for example, by comprising one or more separate controllers that are networked together and operate toward a common purpose (e.g., the process and control described herein). An example of a distributed controller for this purpose is one or more integrated circuits on the chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer), and the two are combined to control the process on the chamber.

[0255] Exemplary systems may include, but are not limited to, plasma etching chambers or modules, deposition chambers or modules, spin cleaning chambers or modules, metal plating chambers or modules, cleaning chambers or modules, bevel edge etching chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, atomic layer deposition (ALD) chambers or modules, atomic layer etching (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, EUV lithography chambers (scanners) or modules, dry development chambers or modules, and any other semiconductor processing systems that may be associated with or used in the manufacture and / or processing of semiconductor wafers.

[0256] As mentioned above, depending on the process steps or plural steps to be performed with recourse to the tool, the controller may communicate with one or more of the following in a semiconductor manufacturing plant: other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, adjacent tools, tools distributed throughout the plant, a master computer, another controller, or a tool used in a material conveying, the tool port used in or to and from the tool port in the material transportation carries the wafers / ports to and from.

[0257] EUVL patterning can be performed using any suitable tool commonly referred to as a scanner, such as the TWINSCAN NXE:3300B® platform supplied by ASML (Veldhoven, The Netherlands). The EUVL patterning tool can be a separate apparatus for the substrate to move in and out for deposition and etching described herein. Alternatively, as described below, the EUVL patterning tool may be a module on a larger multicomponent tool. Figure 6 plots the tool architecture of a semiconductor process cluster with vacuum integrated deposition, EUV patterning, and dry development / etch modules (joined with vacuum transfer modules), which are applicable to implementing the processes described herein. Despite the fact that the process can be performed without such vacuum integration equipment, such equipment may be advantageous in some embodiments.

[0258] Figure 6 plots a tool architecture for a semiconductor process cluster with vacuum integrated deposition and patterning modules (which are interfacing with vacuum transfer modules), which are applicable to implementing the processes described herein. The arrangement of transfer modules used to "transfer" wafers between multiple storage facilities and processing modules may be referred to as a "cluster tool architecture" system. The deposition and patterning modules are vacuum integrated according to the requirements of the specific process. Other modules (e.g. for etching) can also be included in the cluster.

[0259] The vacuum transfer module (VTM) 638 is connected to four processing modules 620a-620d (which can be separately optimized to perform numerous manufacturing processes). For example, treatment modules 620a-620d may be implemented to perform deposition, evaporation, ELD, dry development, etching, stripping, and / or other semiconductor processes. For example, module 620a may be an ALD reactor that may be operated to perform thermal atomic layer deposition as described herein in a non-plasma, for example, a Vector tool available from Lam Research Corporation, Ferrimon Collin, California. Additionally, module 620b may be a PECVD tool, such as Lam Vector®. It should be understood that the diagram is not necessarily drawn to scale.

[0260] Gas chambers 642 and 646 (also referred to as loading chambers or transfer modules) are connected to VTM 638 and patterning module 640. For example, as described above, a suitable patterning module could be the TWINSCAN NXE:3300B® platform supplied by ASML (Felderhofen, Netherlands). This tooling architecture allows workpieces (e.g., semiconductor substrates or wafers) to be transferred under vacuum so as not to react before exposure. Considering the strong light absorption of incident photons by ambient gases (such as H2O, O2, etc.) and the need for a significant reduction in pressure for EUVL, the integration of the deposition module with the lithography tooling is encouraged.

[0261] As described above, this integrated architecture is merely one possible embodiment of the tools used to implement the aforementioned processes. These processes can also be implemented using more conventional standalone EUVL scanners and deposition reactors (e.g., Lam Vector tools), which are either standalone or integrated with other tools (e.g., etching, stripping, etc.) in a cluster architecture (e.g., Lam Kiyo or Gamma tools) as modules, such as those shown in Figure 6, but without integrated patterned modules.

[0262] Gas chamber 642 can be an "output" loading chamber, referring to the transfer of the substrate from VTM 638 for deposition module 620a to patterning module 640, while gas chamber 646 can be an "in" loading chamber, referring to the transfer of the substrate from patterning module 640 back to VTM 638. The in loading chamber 646 can also provide an interface to the outside of the tooling for the entry and exit of the substrate. Each process module has a facet that bonds the module to VTM 638. For example, deposition process module 620a has facet 636. Within each facet, sensors (e.g., sensors 1-18 shown) are used to detect the passage of wafer 626 as it moves between corresponding stations. Patterning module 640 and gas chambers 642 and 646 can similarly accommodate additional facets and sensors (not shown).

[0263] A primary VTM robot 622 transfers wafers 626 between modules (including gas chambers 642 and 646). In one embodiment, robot 622 has one arm, while in another embodiment, robot 622 has two arms, each arm having an end effector 624 to pick up wafers (such as wafer 626) for transfer. A front-end robot 644 is used to transfer wafers 626 from the output gas chamber 642 to the patterning module 640 and from the patterning module 640 to the inlet gas chamber 646. The front-end robot 644 can also transfer wafers 626 between the inlet loading chamber and the outside of the tool for substrate entry and exit. Because the inlet gas chamber module 646 has the ability to match environments between atmospheric and vacuum, wafers 626 can move between two pressure environments without damage.

[0264] It should be noted that EUVL tools typically operate at higher vacuum levels than deposition tools. In this case, it is desirable to increase the vacuum environment of the substrate during the transfer from deposition to the EUV tool to allow the substrate to be degassed before entering the patterning tool. The output gas chamber 642 provides this function by maintaining the transferred wafer at a lower pressure (not exceeding the pressure in the patterning module 640) for a period of time and venting any exhaust gases, ensuring that the optics of the patterning tool 640 are not contaminated by exhaust gases from the substrate. A suitable output gas chamber pressure does not exceed 1E-8 Torr.

[0265] In some embodiments, system controller 650 (which may include one or more physical or logical controllers) controls some or all of the operations of cluster tools and / or their separate modules. It should be noted that the controller may be local to the cluster architecture, located outside the cluster architecture in the manufacturing layer, or remotely connected to the cluster architecture via a network. System controller 650 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 control boards, and other similar components. Instructions for performing appropriate control operations are executed on the processor. These instructions may be stored on memory devices associated with the controller, or may be provided via a network. In some embodiments, the system controller executes system control software.

[0266] System control software may include instructions for controlling the timing of the application and / or magnitude of any state of tool or module operation. System control software can be configured in any suitable manner. For example, it may be written into various process tool component subroutines or control objects to control the operation of process tool components required to implement various process tool processes. System control software may be coded in any suitable computer-readable programming language. In some embodiments, system control software includes input / output control (IOC) sequencing instructions for controlling the aforementioned parameters. For example, each stage of a semiconductor manufacturing process may include one or more instructions executed by a system controller. For example, instructions for setting process conditions for condensation, deposition, evaporation, patterning, and / or etching stages may be included in the corresponding formulation stage.

[0267] In many embodiments, an apparatus for forming a negative pattern mask is provided. The apparatus may include a processing chamber for patterning, deposition, and etching, and a controller including instructions for forming the negative pattern mask. The instructions may include encoding for patterning features in a chemically amplified (CAR) resist on a semiconductor substrate by exposing the surface of a substrate to EUV exposure in the processing chamber, dry developing the photo-patterning resist, and using the patterned resist as a mask to etch an underlayer or stack.

[0268] It should be noted that the computer controlling wafer movement can be located locally within the cluster architecture, or outside the cluster architecture in the manufacturing layer, or at a remote location and connected to the cluster architecture via a network. [Example] [ Example , ] [ 1 , ] [ Includes xenon as a sensitizer , ] [ , ]

[0269] Xenon has a high light absorption cross-section, for example, approximately 1.16E+0.5 cm² / g. Xenon is a gas under standard pressure and temperature conditions, with a density of approximately 0.01 g / cm³. Therefore, xenon in gaseous form can be used as a sensitizer within a membrane.

[0270] As an inert gas, xenon does not interfere with the gas-phase polymerization reaction required for depositing EUV inhibitor materials. However, any xenon physically trapped within a solid-phase PR film may generate primary and secondary photoelectrons. In this way, xenon is used as a sensitizer to provide a sensitized film with enhanced EUV photon collection for bond breaking. Exemplary embodiments including xenon are provided herein.

[0271] In one embodiment, xenon is used within the vapor delivery system. Specifically, xenon can be used as a driving gas for EUV inhibitor materials (or their precursors) in the vapor delivery system and / or as a driving gas for the reactants (e.g., H₂O or other hydroxyl sources, such as alcohols). The driving gas can then be introduced into the deposition chamber.

[0272] In another embodiment, xenon is used as a bubbling gas within the vapor delivery system. For example, xenon can be bubbled through a liquid form of an EUV inhibitor material (or its precursor), and the xenon vapor can be directed into the deposition chamber. In another example, xenon can be bubbled through a liquid form of a reactant, and the resulting xenon vapor can be directed into the deposition chamber.

[0273] In one embodiment, xenon-based gases are used as diluent gases, which can be used to dilute any gas streams used within the vapor delivery system connected to the deposition chamber. The gas streams may include any useful compounds, such as EUV inhibitor materials, EUV inhibitor material precursors, or reactive substances in vapor form; and the diluent can be used to dilute any of these gas streams.

[0274] In one embodiment, the deposition process is divided into smaller increments within the deposition chamber. For example, a first increment may include delivering EUV inhibitor material or a precursor thereof, while a second increment may include exposure to xenon. The deposition process may then include alternating first and second increments until the desired film is deposited. In some embodiments, the second increment may include providing xenon at a higher pressure than that used during deposition (e.g., 10 to 100 times higher than the deposition process pressure). In a particular embodiment, the second increment includes providing xenon at a pressure of about 100 millitorres to 1000 tors (e.g., about 100 millitorres to 100 tors).

[0275] In another embodiment, a PR layer comprising an EUV resist material is treated with PAB in the presence of xenon. In some embodiments, the PAB step is performed at high temperatures in a Xe-rich environment. For PAB, non-limiting temperatures include about 90°C to 250°C, for example, 90°C to 190°C, and about 170°C to 250°C or higher, for example, 190°C to 240°C. In other embodiments, the PAB step can be performed by bombarding plasma in xenon under a downstream discharge rich in Xe ions and radicals in the absence of photons.

[0276] In one embodiment, the EUV inhibitor material (or its precursor) is degassed before xenon is injected into the deposition chamber. Degassedness can be achieved by employing a PAB step and / or by applying a vacuum to provide lower pressure. Xenon injection can be performed under any useful conditions to promote injection efficiency and density, such as injection at high pressure and / or low temperature. In some embodiments, xenon injection is performed at high pressure, followed by a temperature reduction.

[0277] In another embodiment, the deposition of a tunable resist material promotes increased xenon incorporation. For example, in one embodiment, deposition may include conditions that provide a lower density of EUV resist material in the PR film (e.g., cryogenic deposition), thereby increasing xenon incorporation into the film (e.g., through any of the methods described herein, such as providing xenon as a propellant gas, bubbling gas, diluent, ambient gas, injection, etc.).

[0278] In one embodiment, a residual amount of xenon can be provided within the deposition chamber, thus providing a background amount of xenon during the deposition of the EUV resist material. This residual amount can be achieved by cleaning the deposition chamber using xenon-infused plasma chemistry in a post-deposition process. In this way, the cleaning operation specifically provides a background amount of xenon within the deposition chamber for the next product wafer to be deposited.

[0279] In another embodiment, xenon gas can be reused and recycled. For example, unreacted xenon can be collected before, after, or during the post-deposition or coating baking process; and the collected xenon gas can be reused in any of the processes described herein.

[0280] In one embodiment, xenon has a gradient density within the sensitized film. In one embodiment, the xenon density gradually decreases from heavier at the bottom of the film to lighter at the top. Generally, the film has lower EUV absorption at the bottom, and the presence of additional xenon at the bottom provides additional EUV absorption compared to a film without xenon. By controlling the xenon density gradient within the film, the sensitized film can achieve uniform EUV absorption throughout its entire thickness.

[0281] These gradients can be implemented in any useful manner. For example, increased xenon can be deposited by increasing the flow rate of xenon in the vapor delivery system (e.g., as a driving gas, bubbling gas, or diluent), and decreased xenon can be deposited by decreasing the flow rate of xenon or by diluting the xenon flow with an inert carrier gas or an inert non-photoactivated carrier gas (e.g., any of those described herein, such as He or Ar).

[0282] In another embodiment, any useful form of xenon can be delivered during deposition or PAB. In one instance, heavier (but radioactively stable) isotopes of xenon, such as 133Xe or 136Xe, can be used. It is undesirable to be limited by the mechanism by which heavier isotopes are incorporated into the PR film when used as a propellant gas, a bubbling gas, a diluent, or an interleaved exposure gas during deposition. In another instance, lighter isotopes of xenon, such as 129Xe, can be used. It is undesirable to be limited by the mechanism by which lighter isotopes are diffused into the deposited PR film when used as an ambient gas during PAB.

[0283] In a further embodiment, any of the processes described herein (e.g., in this example) may be combined to provide a sensitized membrane. [ Example , ] [ 2 , ] [ It contains iodine as a sensitizer. , ] [ , ]

[0284] Iodine has a high light absorption cross section, for example, approximately 1.10E+05 cm² / g. Iodine is a gas under standard pressure and temperature conditions, with a density of approximately 4.93 g / cm³. Furthermore, iodine can be incorporated as a heteroatom in EUV inhibitor materials or their precursors. Therefore, incorporating iodine as a sensitizer within the membrane can utilize iodine-containing compounds in gaseous form or iodine-containing compounds provided in vapor form carried by an inert carrier gas.

[0285] In one embodiment, the deposition process is divided into smaller increments within the deposition chamber. For example, a first increment may include delivery of an EUV inhibitor material or a precursor thereof, while a second increment may include exposure to an iodine-containing compound (e.g., HI or I2). The deposition process may then include alternating first and second increments until the desired film is deposited. In some embodiments, the second increment may include providing the iodine-containing compound at a higher pressure than that used during deposition (e.g., 10 to 100 times higher than the deposition process pressure). In a particular embodiment, the second increment includes providing the iodine-containing compound at a pressure of about 100 millitors to 1000 tors (e.g., about 100 millitors to 100 tors).

[0286] In another embodiment, a PR layer comprising an EUV resist material is treated with PAB in the presence of an iodine-containing compound. In some embodiments, the PAB step is performed at high temperatures in an iodine-rich environment. For PAB, non-limiting temperatures include about 90°C to 250°C, for example, 90°C to 190°C, and about 170°C to 250°C or higher, for example, 190°C to 240°C. In other embodiments, the PAB step can be performed by bombarding plasma in iodine under a downstream discharge rich in I ions and free radicals in the absence of photons.

[0287] In one embodiment, a residual amount of iodine may be provided within the deposition chamber, thus providing a background amount of iodine during the deposition of the EUV resist material. This residual amount can be achieved by cleaning the deposition chamber using iodine-infused plasma chemistry (e.g., HI-based plasma chemistry) in a post-deposition process. In this way, the cleaning operation specifically provides a background amount of iodine within the deposition chamber for the next product wafer to be deposited.

[0288] In one embodiment, the EUV inhibitor material (or its precursor) is degassed, followed by the injection of an iodine-containing compound (e.g., I₂ or HI) into the deposition chamber. Degassed can be performed using a PAB step and / or by applying a vacuum to provide a lower pressure. Injection can be performed under any useful conditions to promote injection efficiency and density, such as injection at high pressure and / or low temperature. In some embodiments, the injection of the iodine-containing compound is performed at high pressure, followed by a decrease in temperature.

[0289] In another embodiment, the deposition of a tunable resist material is used to promote increased incorporation of iodine-containing compounds (e.g., HI). For example, in one embodiment, deposition may include conditions that provide a lower density of EUV resist material in the PR film (e.g., low-temperature deposition), thereby increasing the incorporation of iodine-containing compounds into the film (e.g., by any of the methods described herein, such as providing the iodine-containing compound as a driving gas, foaming gas, diluent, ambient gas, injection, etc.).

[0290] In one embodiment, the iodine-containing compound is an EUV inhibitor material or a precursor comprising one or more iodine substitutions. In one embodiment, the precursor comprises iodine substitution at the β-position of an alkyl group contained in the precursor. In another embodiment, the precursor comprises iodine substitution at the α-position of an alkyl group contained in the precursor.

[0291] In one embodiment, the iodine-containing compound has a gradient density within the sensitized membrane. In one embodiment, the density of iodine gradually decreases from heavier at the bottom of the membrane to lighter at the top. Generally, the membrane has lower EUV absorption at the bottom, and the presence of additional iodine at the bottom provides additional EUV absorption compared to a membrane without iodine. By controlling the density gradient of iodine within the membrane, the sensitized membrane can achieve uniform EUV absorption throughout its entire thickness.

[0292] These gradients can be implemented in any useful manner. For example, increased iodine can be deposited by increasing the flow rate of the iodine-containing compound within the steam delivery system (e.g., as a driving gas, bubbling gas, or diluent), and reduced iodine can be deposited by decreasing the flow rate of the iodine-containing compound or by diluting the iodine-containing compound gas stream with an inert carrier gas or an inert non-photoactivated carrier gas (e.g., any of those described herein, such as He or Ar).

[0293] In another embodiment, the iodine-containing compound (e.g., I2 or HI) can be reused and recycled. For example, unreacted iodine-containing compounds can be collected before, after, or during the post-deposition or coating baking process; and the collected iodine-containing compounds can be reused in any of the processes described herein.

[0294] In a further embodiment, any of the processes described herein (e.g., in this example) may be combined to provide a sensitized membrane. [ in conclusion , ] [ , ]

[0295] While the foregoing embodiments have been described in detail for clarity of purpose, it will be apparent that certain changes and modifications may be made within the scope of the accompanying 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 to avoid unnecessarily obscuring the disclosed embodiments. Furthermore, although the disclosed embodiments are described in conjunction with specific examples, it will be understood that the specific examples are not intended to limit the disclosed embodiments. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatuses of this embodiment. Accordingly, this embodiment should be considered illustrative rather than restrictive, and the embodiments are not limited to the details given herein.

[0296] 100: First-stage sedimentation chamber 101: Substrate, First diluent 102: Sensitized membrane, first propellant gas 103: Second propellant gas 104: Second diluent 105: Precursor 106: Relative reactants 110: Pump 120: Cold Trap 122: Excrement 124: EUV sensitizer 130: First pump 140: Second pump 150: Second-stage sedimentation chamber 151: Third diluent 152: Third Propellant Gas 153: Fourth Propellant Gas 154: Fourth diluent 155: Precursor 156: Relative reactants 200: Method 202: Steps 203: Steps 204: Steps 206: Steps 208: Steps 210: Steps 212: Steps 220: Method 222: Steps 223: Steps 224: Steps 226: Steps 228: Steps 230: Steps 232: Steps 240: Method 242: Steps 244: Steps 245: Steps 246: Steps 248: Steps 250: Steps 252: Steps 254: Steps 300: Process Station 301a: Reactant Delivery System 302: Main body of the process chamber 303: Vaporization point 304: Mixing container 305: Connection 306: Spray head 307: Plasma 308: Base 310: Heater 312:Substrate 314: Radio Frequency Power Supply 316: Matching network 318: Butterfly Valve 320: Mixing container inlet valve 350: Computer Controller 400: Multi-site processing tool 402: Loading Room at the Station 404: Departure Loading Room 406: Robot 408: Teleport Box 410: Atmospheric port 412: Base 414: Processing Chamber 416: Chamber transfer port 418: Base 450: System Controller 452: Processor 454: High-capacity storage devices 456: Memory device 458: System Control Software 490: Wafer Handling System 500: Inductively Coupled Plasma Equipment 501: Chamber wall 502: Upper secondary chamber 503: Lower secondary chamber 511: Window 517: Suction Cup 519: Semiconductor Wafer 521: Matching Circuit 522: Port 523: Radio Frequency Power Supply 525: Connection 527: Connection 530: System Controller 533: Coil 539: Matching Circuit 540: Vacuum pump 541: Radio Frequency Power Supply 543: Connection 545: Connection 549: Faraday Shield 550: System controller, plasma grid 560: Main airflow inlet 570: Side airflow inlet 600: Semiconductor Process Cluster Tool Architecture 620a: Processing Module 620b: Processing Module 620c: Processing Module 620d: Processing Module 622: Vacuum Transfer Module Robot 624: End effector 626: Wafer 636: End face 638: Vacuum Transfer Module 640: Patterned Module 642: Air Chamber 644: Front-end robot 646: Air Chamber 650: System Controller

Claims

1. A stack, comprising: A semiconductor substrate having a top surface; And a sensitizing film disposed on the top surface of the semiconductor substrate, wherein the sensitizing film includes an extreme ultraviolet (EUV) resist material and an EUV sensitizer dispersed throughout the sensitizing film, wherein the EUV resist material includes a metal.

2. The stack as described in claim 1, wherein the EUV sensitizer comprises iodine or xenon.

3. The stack as described in claim 2, wherein the EUV sensitizer is I2, HI, an organometallic precursor containing an iodine-substituted alkyl group, a precursor thereof, 133Xe, 136Xe, 129Xe, or any combination of such xenon isotopes.

4. A stack, comprising: A semiconductor substrate having a top surface; And a sensitizing film disposed on the top surface of the semiconductor substrate, wherein the sensitizing film includes an extreme ultraviolet (EUV) resist material and an EUV sensitizer containing xenon, wherein the EUV resist material includes a metal.

5. The stack as described in claim 4, wherein the EUV sensitizer is 133Xe, 136Xe, 129Xe, or any combination thereof.

6. The stack as described in claims 1-5, wherein the EUV inhibitor material comprises an organometallic material, and wherein the organometallic material optionally further comprises iodine-substituted alkyl groups.

7. A method for forming a sensitized film, the method comprising: A semiconductor substrate is provided within a cavity; The device also delivers an extreme ultraviolet (EUV) resist material or its precursor and an EUV sensitizer to the chamber, wherein the EUV resist material or its precursor and the EUV sensitizer can be delivered sequentially or simultaneously in any order, and wherein the EUV resist material or its precursor and the EUV sensitizer are provided in gaseous form, thereby forming the sensitization film on one of the top surfaces of the semiconductor substrate, wherein the EUV resist material comprises a metal.

8. The method of forming a sensitized film as described in claim 7, wherein the EUV sensitizer is provided as a driving gas containing vapor of the EUV inhibitor material or its precursor, as a foaming gas of the EUV inhibitor material or its precursor, or as a diluent delivered to the chamber.

9. The method of forming a sensitized film as described in claim 7, wherein the delivery further comprises: One or more reactants are delivered to the chamber.

10. The method of forming a sensitized film as described in claim 9, wherein the EUV sensitizer is provided as a driving gas for the one or more relative reactants.

11. A method for forming a sensitized film, the method comprising: A film is deposited on a top surface of a semiconductor substrate, wherein the film includes an extreme ultraviolet (EUV) resist material, wherein the EUV resist material comprises a metal; and the film is heated in a chamber in the presence of an EUV sensitizer in gaseous form, thereby forming a sensitized film on the top surface of the semiconductor substrate, wherein the sensitized film includes the EUV resist material and the EUV sensitizer.

12. The method of forming a sensitized film as described in claim 11, wherein the deposition comprises thermal atomic layer deposition, spin coating deposition, electron beam evaporation, or a combination thereof.

13. A method for forming a sensitized film, the method comprising: Provides a chamber containing at least one residual amount of an extreme ultraviolet (EUV) sensitizer; A semiconductor substrate is provided within the cavity; An EUV resist material is delivered to the chamber, thereby forming the sensitization film on the top surface of the semiconductor substrate, wherein the sensitization film includes the EUV resist material and the EUV sensitizer, wherein the EUV resist material contains a metal.

14. The method of forming a sensitized film as described in claims 7-13, further comprising, after the delivery: patterning the sensitized film in a vacuum environment by EUV exposure in the wavelength range of about 10 nm to about 20 nm, wherein the EUV exposure generates additional primary and / or secondary photoelectrons in the sensitized film compared to a control film that does not contain the EUV sensitizer.

15. The method of forming a sensitized film as described in claim 14, further comprising, if present, capturing the EUV sensitizer present in gaseous form within the chamber after the delivery and / or before the patterning.

16. The method of forming a sensitized film as described in claim 15, wherein the trapping includes employing a cold trap to recover the EUV sensitizer in gaseous form.

17. The method of forming a sensitized film as described in claims 7-13, wherein the EUV sensitizer comprises iodine or xenon.

18. The method of forming a sensitized film as described in claim 17, wherein the EUV sensitizer is I₂, HI, an organometallic precursor containing an iodine-substituted alkyl group, 133Xe, 136Xe, 129Xe, or any combination of such xenon isotopes.

19. An apparatus for depositing a sensitized film, the apparatus comprising: A deposition module includes a chamber for depositing an extreme ultraviolet (EUV) resist material and an EUV sensitizer into a sensitized film, wherein the EUV resist material or its precursor and the EUV sensitizer are provided in gaseous form, and wherein the EUV resist material comprises a metal; a patterning module includes an EUV lithography tool having a radiation source with a wavelength of less than 30 nm; a developing module includes a chamber for developing the sensitized film; and a controller including one or more memory devices, one or more processors, and system control software programmed with instructions for performing film deposition, the instructions including instructions for: depositing the sensitized film on a top surface of a semiconductor substrate in the deposition module, wherein the sensitized film includes the EUV resist material and the EUV sensitizer; and directly exposing the film to EUV in a vacuum environment with a wavelength range of about 10 nm to about 20 nm at a wavelength of less than 30 nm. The sensitized film is patterned at a resolution of nm, thereby forming a pattern within the sensitized film; and the sensitized film is developed in the developing module to provide the pattern within the sensitized film.

20. The apparatus for depositing a sensitized film as described in claim 19, wherein, According to these instructions, the EUV inhibitor material or its precursor and the EUV sensitizer may be delivered sequentially or simultaneously in any order.

21. The apparatus for depositing a sensitized film as described in claim 19, wherein, According to these instructions, in the deposition module, the EUV sensitizer is provided as a driving gas for the EUV inhibitor material or its precursor, a foaming gas containing vapor of the EUV inhibitor material or its precursor, or a diluent delivered to the chamber.

22. An apparatus for depositing a sensitized membrane, the apparatus comprising: A deposition module includes a heater and a chamber for depositing an extreme ultraviolet (EUV) resist material into a film, wherein the EUV resist material comprises a metal; a patterning module includes an EUV lithography tool having a radiation source with a wavelength of less than 30 nm; a development module includes a chamber for developing the sensitized film; and a controller including one or more memory devices, one or more processors, and system control software programmed with instructions for performing film deposition, the instructions including instructions for: in the deposition module, depositing the film on a top surface of a semiconductor substrate and heating the film using the heater in the presence of an EUV sensitizer in gaseous form, thereby forming the sensitized film on the top surface of the semiconductor substrate, wherein the sensitized film includes the EUV resist material and the EUV sensitizer; in the patterning module, directly exposing the film to EUV in a wavelength range of about 10 nm to about 20 nm in a vacuum environment at a wavelength of less than 30 nm. The sensitized film is patterned at a resolution of nm, thereby forming a pattern within the sensitized film; and the sensitized film is developed in the developing module to provide the pattern within the sensitized film.

23. An apparatus for depositing a sensitized membrane, the apparatus comprising: A deposition module includes a chamber for depositing an extreme ultraviolet (EUV) resist material into a film, wherein the chamber includes at least a residual amount of an EUV sensitizer; and wherein the EUV resist material comprises a metal; a patterning module includes an EUV lithography tool having a radiation source with a wavelength of less than 30 nm; a development module includes a chamber for developing the sensitized film; and a controller including one or more memory devices, one or more processors, and system control software programmed with instructions for performing film deposition, the instructions including instructions for: depositing the sensitized film on a top surface of a semiconductor substrate in the deposition module, wherein the sensitized film includes the EUV resist material and the EUV sensitizer; and directly exposing the film to EUV in a vacuum environment with a wavelength range of about 10 nm to about 20 nm at a wavelength of less than 30 nm. The sensitized film is patterned at a resolution of nm, thereby forming a pattern within the sensitized film; and the sensitized film is developed in the developing module to provide the pattern within the sensitized film.

24. The apparatus for depositing a sensitized film as described in claims 19-23, further comprising: A recovery module includes a trap, wherein the recovery module is fluidly connected to the deposition module, and wherein the instructions further include: capturing the EUV sensitizer, which is present in gaseous form, within the chamber of the deposition module in the recovery module.

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