Metal chelating agents for developing metal-containing photoresists

Abstract

The present disclosure relates to the use of metal chelating agents to treat exposed photoresist films. In certain embodiments, the metal chelating agents are used to improve patterning quality by removing interfacial regions located between exposed and unexposed regions or located within exposed regions.

Description

[Technical Field]

[0001] Reference A PCT request form is filed concurrently with this specification as part of this application. Each application on which this application claims interest or priority, as identified in the concurrently filed PCT request form, is incorporated herein by reference in its entirety for all purposes. This application claims interest based on U.S. Provisional Patent Application No. 62 / 705,855, filed July 17, 2020, which is incorporated herein by reference in its entirety.

[0002] This disclosure relates to the use of metal chelating agents for processing exposed photoresist films. In certain embodiments, metal chelating agents are used to improve patterning quality by removing interface regions located between or within exposed regions. [Background technology]

[0003] The background art provided herein is intended to provide a general overview of the background of this technology. The works of the inventors named herein, to the extent described in this background art, are not recognized as prior art, either explicitly or implicitly, with respect to this technology, along with any manner of description that would not ordinarily be considered prior art at the time of filing.

[0004] Thin film patterning in semiconductor processing is often a crucial step in semiconductor manufacturing. Patterning includes lithography. In photolithography (such as 193nm lithography), a pattern is printed onto a photosensitive photoresist by emitting photons from a photon source onto a mask. This triggers a chemical reaction in the photoresist, which, after development, removes specific parts of the photoresist to form the pattern.

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

[0006] Extreme ultraviolet (EUV) lithography can extend lithography techniques by moving to imaging source wavelengths shorter than those achievable with other photolithography methods. EUV light sources with wavelengths of approximately 10–20 nm or 11–14 nm (e.g., 13.5 nm) can be used with modern lithography tools (also called scanners). EUV radiation is strongly absorbed by a wide range of solid and fluid materials, including quartz and water vapor, and is therefore applied in a vacuum. [Overview of the project]

[0007] This disclosure relates to the use of one or more metal chelating agents during the development (e.g., wet development) of metal photoresists (PRs). During lithographic exposure of organometallic PRs, an interface region may exist between the lithographically exposed and unexposed regions. As discussed herein, this interface region can be characterized as a region of abrupt transition from the most exposed region to the completely unexposed region. Therefore, in this interface region, the composition of the PR may contain various partial reaction products that differ from those present in the most exposed region and those present in the completely unexposed region. Such reaction products may lead to roughness after wet development. Furthermore, this interface region may extend over a short distance (e.g., 1 or 2 nanometers), and the general composition within this interface region is approximately the composition required at the dose threshold of wet development.

[0008] Weakly bonded metal species may be present in this interface region. As described herein, this disclosure provides for the removal of such metal species using metal chelating agents, which can improve the resulting patterning quality, particularly with respect to line width roughness (LWR) and / or line edge roughness (LER).

[0009] Accordingly, in a first embodiment, the present disclosure features a method comprising the steps of: providing a radiation-patterned film (e.g., an exposed film) having an interface region; and developing the radiation-patterned film in the presence of a metal chelating agent (e.g., or two or more different metal chelating agents), wherein the metal chelating agent is configured to bond to one or more radiation-exposed metal centers in the interface region. In some embodiments, the radiation-exposed metal centers are weakly bonded metal species (e.g., characterized by 1, 2, or 3 metal-oxygen bonds). The interface region is located between a radiation-exposed region and a radiation-unexposed region, or (e.g., a highly exposed region and To a low degree exposure did The interface region may be located within the radiation exposure region (between the regions). In some embodiments, the interface region comprises an interface, or transition region, located between a highly exposed region and an unexposed region, or between a high-exposure region and a low-exposure region.

[0010] In certain embodiments, the exposure film or radiation-patterned film includes an extreme ultraviolet (EUV) sensitive film. In other embodiments, the exposure film or radiation-patterned film is characterized by having an EUV-exposed region, an EUV-unexposed region, and an interface region located between the EUV-exposed and EUV-unexposed regions, upon exposure to EUV radiation. In yet another embodiment, the interface region includes a region that is less exposed to EUV radiation (for example, compared to a region that is highly exposed to EUV radiation). In certain embodiments, the interface region is located within the EUV-exposed region.

[0011] In some embodiments, as used herein, the “radiation-exposed region” may include regions where exposure to radiation can vary. For example, the dose curve (a function of distance) within the radiation-exposed region may be nonlinear, resulting in some areas of the region being exposed to higher radiation doses and others to lower doses. Since the degree of radiation dose can affect the degree of reaction within the PR, various reaction products may be present within the radiation-exposed region. Therefore, in some embodiments, the radiation-exposed region can be considered to include an interface region that transitions abruptly from the most exposed region to the least exposed region.

[0012] In some embodiments, the development step further includes a step of removing interfacial regions. Such a removal step can provide improved LWR and / or LER compared to development without a metal chelating agent (characterized by a reduction in high-frequency noise determined by power spectral density measurements to distinguish different line roughness sources, such as high, medium, and low-frequency sources). For example, the use of a chelating agent can reduce high to medium frequency roughness by removing local perturbations to the line shape of the power spectral density curve. In certain embodiments, the development step includes a step of providing a metal chelating agent together with a solvent or solvent mixture (e.g., any of those described herein).

[0013] In other embodiments, the developing step further includes a step of using a solvent or solvent mixture that preferentially removes radiation-exposed regions compared to radiation-unexposed regions. In some embodiments, the metal chelating agent is soluble in the solvent or solvent mixture. In certain embodiments, the metal chelating agent preferentially binds to radiation-exposed metal centers in the interface region compared to metal centers present in radiation-unexposed regions.

[0014] In some embodiments, the metal chelating agent is a dicarbonyl (e.g., 1,3-diketone), diol, or carboxylic acid (e.g., R A1 -CO2H, here, R A1is H, optionally substituted alkyl, optionally substituted hydroxyalkyl, optionally substituted hydroxyaryl, optionally substituted carboxyalkyl, optionally substituted carboxyaryl, or optionally substituted aryl), diacid, triacid, hydroxycarboxylic acid, hydroxamic acid (e.g., R A1 -C(O)NR A2 OH, where each of R A1 and R A2 is independently H, optionally substituted alkyl, or optionally substituted aryl), hydroxypyrone, hydroxyketone (e.g., hydroxypyridinone, hydroxypyrimidinone, or hydroxypyrone), or a salt thereof. In other embodiments, the metal chelating agent includes formic acid, citric acid, acetylacetone, salicylic acid, catechol, or ascorbic acid.

[0015] In other embodiments, the metal chelating agent has the structure of the following chemical formula (I), (II), or (III):

Chemical formula

Chemical formula

Chemical formula

[0016] In some embodiments, the metal chelating agent comprises a plurality of parts arranged on a skeleton, where the plurality of parts are selected from hydroxyl, carboxyl, amide, amino, and oxo. Non-limiting parts include one or more of monovalent or polyvalent dicarbonyl, diol, carboxylic acid, diacid, triacid, hydroxycarboxylic acid, hydroxamic acid, hydroxylactone, hydroxyketone, or salts thereof.

[0017] In some embodiments, the radiation-exposed metal center includes a transition metal. Non-limiting metal centers include, for example, tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), tantalum (Ta), cesium (Cs), indium (In), molybdenum (Mo), or hafnium (Hf).

[0018] The exposure film or radiation-patterned film may be formed from any useful metal precursor (e.g., any of those described herein). In certain embodiments, the metal precursor has a structure having the following chemical formula (Iv): M a R b (IV) Here, M is a metal (e.g., Sn, Te, Bi, Sb, Ta, Cs, In, Mo, or Hf, or any of those specified herein), and each R is independently H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, anionic ligand, neutral ligand, or polydentate ligand, where a≧1 (e.g., a is 1, 2, or 3) and b≧1 (e.g., b is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12).

[0019] In a second embodiment, the disclosure includes a method (e.g., a resist utilization method) to provide a patterning radiation-sensitive film as a resist film, comprising the steps of: depositing a metal precursor onto the surface of a substrate; patterning the resist film by patterning radiation exposure; and developing the exposed film in the presence of a metal chelating agent and a solvent. In some embodiments, the deposition step includes the use of a counter-reactant (an oxygen-containing counter-reactant, such as any of those described herein).

[0020] In other embodiments, the patterning step provides an exposure film having one or more radiation-exposed regions, one or more radiation-unexposed regions, and an interface region positioned between at least one radiation-exposed region and at least one radiation-unexposed region. In some embodiments, radiation exposure (e.g., patterning radiation exposure) includes EUV exposure having wavelengths in the range of about 10 nm to about 20 nm in a vacuum atmosphere.

[0021] In further embodiments, the development step removes the interface region and either the radiation-exposed or radiation-unexposed region. In some embodiments, the pattern includes reduced LER and / or LWR compared to a pattern developed without a metal chelating agent.

[0022] In some embodiments, the metal chelating agent is configured to preferentially remove the interface region (e.g., compared to the radiation-exposed region and / or the non-radiation-exposed region). In further embodiments, the solvent is configured to preferentially remove either the radiation-exposed region or the non-radiation-exposed region (e.g., compared to the interface region).

[0023] In some embodiments, the method further comprises the step of removing the metal chelating agent and / or metal-chelate complex from the film (for example, after development).

[0024] In a third aspect, the disclosure includes an apparatus (for example, an apparatus for forming a resist film) comprising: a deposition module; a patterning module; a developing module; one or more memory devices; one or more processors; and a controller having system control software coded with instructions including machine-readable instructions.

[0025] In some embodiments, the deposition module comprises a chamber for depositing a patterning radiation-sensitive film (e.g., an EUV-sensitive film). In other embodiments, the patterning module comprises a photolithography tool having a radiation source with a wavelength of less than 300 nm (wherein the radiation source may be a radiation source with a wavelength of less than 30 nm). In yet another embodiment, the developing module comprises a chamber for developing a resist film.

[0026] In certain embodiments, the controller instruction includes a machine-readable instruction to deposit a metal precursor onto the upper surface of a semiconductor substrate to form a patterning radiation-sensitive film as a resist film (e.g., in a deposition module). In other embodiments, the controller instruction includes a machine-readable instruction to form an interface region located between at least one radiation-exposed region and at least one radiation-unexposed region by directly patterning the resist film by patterning radiation exposure with a resolution of less than 300 nm (e.g., or less than 30 nm). In certain embodiments, the interface region is a region that is less exposed to EUV radiation (e.g., compared to another region that is highly exposed to EUV radiation), or a transition region located between at least one EUV-exposed region and at least one EUV-unexposed region, or at least one highly EUV-exposed region and at least one To a low degree EUV exposure did It is a transitional area placed between different domains.

[0027] In some embodiments, the controller instructions include machine-readable instructions for developing the exposure film in the presence of a metal chelating agent and a solvent (for example, in a developing module). In certain embodiments, development removes interface regions and at least one of radiation-exposed or radiation-unexposed regions to provide a pattern within the resist film. In other embodiments, the machine-readable instructions include instructions for removing interface regions. In yet another embodiment, the machine-readable instructions include instructions for removing EUV-exposed or EUV-unexposed regions.

[0028] In any embodiment of this specification, the metal chelating agent is a dicarbonyl (e.g., 1,3-diketone (such as acetylacetone)), hydroxyalkyl, hydroxyaryl, diol (e.g., glycol, catechol, etc.), carboxylic acid (e.g., formic acid or citric acid, etc.). A1 -CO2H, here, RA1 (where H is an optionally substituted alkyl, optionally substituted hydroxyalkyl, optionally substituted carboxyalkyl, optionally substituted aryl, or optionally substituted aryl), diacids, triacids, hydroxycarboxylic acids (e.g., phenolic acids (such as salicylic acid)), hydroxamic acids (e.g., R) A1 -C(O)NR A2 OH, here, R A1 and R A2 Each of these independently comprises H, optionally substituted alkyl, or optionally substituted aryl, hydroxylactone (e.g., ascorbic acid), hydroxyketone (e.g., hydroxypyridinone, hydroxypyrimidone, or hydroxypyrone, such as those having the structure of chemical formulas (I), (II), or (III) as described herein), or salts thereof. In other embodiments, the metal chelating agent comprises a plurality of parts arranged on a skeleton, where the plurality of parts are selected from hydroxyl, carboxyl, amide, amino, and oxo. Non-limiting parts include one or more of monovalent or polyvalent dicarbonyl, diol, carboxylic acid, diacid, triacid, hydroxycarboxylic acid, hydroxamic acid, hydroxylactone, hydroxyketone, or salts thereof.

[0029] In any embodiment of this specification, the exposure film or patterning radiation-sensitive film comprises a metal oxide film or an organometallic oxide film or an organometallic material.

[0030] In any embodiment of this specification, the exposure film or patterned radiation-sensitive film includes an EUV-sensitive film.

[0031] In any embodiment of this specification, the exposure film or patterning radiation-sensitive film comprises a metal having a high patterning radiation absorption cross-section. In certain embodiments, the metal has a high EUV absorption cross-section. In other embodiments, the metal layer comprises tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), tantalum (Ta), cesium (Cs), indium (In), molybdenum (Mo), or hafnium (Hf), as well as combinations thereof.

[0032] In any embodiment of this specification, the metal precursor comprises a structure having the chemical formula (IV), (V), (Va), (VI), (VII), (VIII), (IX), (X), or (XI) as described herein.

[0033] In any embodiment of this specification, the deposition step includes providing or depositing a metal precursor in vapor form. In other embodiments, the deposition step includes providing a reactant in vapor form. In specific embodiments, the deposition step includes chemical vapor deposition (CVD), atomic layer deposition (ALD), or molecular layer deposition (MLD), as well as plasma-enhanced forms thereof.

[0034] In any embodiment of this specification, the step of depositing a metal layer further includes the step of providing a reactant. Non-limiting reactants include oxygen-containing reactants such as O2, O3, water, peroxides, hydrogen peroxide, oxygen plasma, water plasma, alcohols, dihydroxy alcohols, polyhydroxy alcohols, fluorinated dihydroxy alcohols, fluorinated polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, as well as combinations thereof. Further details will be described below.

[0035] definition As used interchangeably herein, “acyloxy” or “alkanoyloxy” means an acyl group or alkanoyl group as defined herein, bonded to a parent group via an oxy group. In certain embodiments, the alkanoyloxy is -OC(O)-Ak, where Ak is an alkyl group as defined herein. In some embodiments, the unsubstituted alkanoyloxy is C 2-7 It is an alkanoyl group. An example of an alkanoyl group is acetoxy.

[0036] "Alkenyl" is an optionally substituted C having one or more double bonds. 2-24 It means alkyl group. An alkenyl group is a cyclic group (for example, C 3-24 The alkenyl group may be cycloalkenyl or acyclic. Furthermore, the alkenyl group may be substituted or unsubstituted. For example, the alkenyl group may be substituted with one or more substituents described herein for alkyl groups.

[0037] "Alkenylene" means the polyvalent (e.g., divalent) form of an alkenyl group as defined herein. The alkenylene group may be substituted or unsubstituted. For example, the alkenylene group may be substituted with one or more substituents for alkyl groups as described herein.

[0038] "Alkoxy" means -OR, where R is an optionally substituted alkyl group as described herein. Examples of alkoxy groups include methoxy, ethoxy, butoxy, and trihaloalkoxy (such as trifluoromethoxy). The alkoxy group may be substituted or unsubstituted. For example, the alkoxy group may be substituted with one or more substituents as described herein for alkyl groups. An example of an unsubstituted alkoxy group is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 Contains an alkoxy group.

[0039] "Alkyl" and the prefix "alk" refer to branched or unbranched saturated hydrocarbon groups with 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), cyclopropyl, n-butyl (n-Bu), isobutyl (i-Bu), s-butyl (s-Bu), t-butyl (t-Bu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. Alkyl groups are cyclic (e.g., C 3-24 The alkyl group may be cycloalkyl or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may include haloalkyl groups, in which the alkyl group is substituted with one or more halo groups, as described herein. In another example, the alkyl group may be substituted with substituents 1, 2, 3, or 4 (in the case of alkyl groups with two or more carbons) independently selected from the following group: (1)C 1-6 Alkoxy (e.g., -O-Ak, where Ak is an optionally substituted C) 1-6 (1) Alkyl), (2) Amino (e.g., NR N1 R N2 , here, R N1 and R N2 Each of them is independent and is H or an optionally substituted alkyl, or R N1 and R N2 (1) each forms a heterocyclyl group with the nitrogen atom to which it is bonded), (2) aryl-yl, (3) arylalkoxy (e.g., -O-Lk-Ar, where Lk is the divalent form of an optionally substituted alkyl and Ar is the optionally substituted aryl), (4) aryloyl (e.g., -C(O)-Ar, where Ar is the optionally substituted aryl), (5) aryloyl (e.g., -C(O)-Ar, where Ar is the optionally substituted aryl), (6) cyano (e.g., -CN), (7) carboxyaldehyde (e.g., -C(O)H), (8) carboxyl (e.g., -CO2H), (9) C 3-8 Cycloalkyl (e.g., monovalent saturated or unsaturated non-aromatic cyclic C 3-8(10) Hydrocarbon group), (11) Halo (e.g., F, Cl, Br, or I), (12) Heterocyclyl (e.g., a five-, six-, or seven-membered ring containing one, two, three, or four non-carbon heteroatoms (such as nitrogen, oxygen, phosphorus, sulfur, or halo) unless otherwise specified), (13) Heterocyclyloxy (e.g., -O-Het, where Het is a heterocyclyl as described herein), (14) Heterocyclyl (e.g., -C(O)-Het, where Het is a heterocyclyl as described herein), (15) Hydroxyl (e.g., -OH), (16) N-protected amino, (17) Nitro (e.g., NO2), (18) Oxo (e.g., =O), (19) -CO2R A , here, R A (a)C 1-6 Alkyl, (b)C 4-18 Aryl, and (c)(C 4-18 Ariel)C 1-6 Selected from the group consisting of alkyl (for example, -Lk-Ar, where Lk is the divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl), (19)-C(O)NR B R C , here, R B and R C Each of them is independent, (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)(C 4-18 Ariel)C 1-6 Selected from the group consisting of alkyl groups (e.g., -Lk-Ar, where Lk is the divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl group), as well as (20)-NR G R H , here, R G and R H Each of these is independent of (a) hydrogen, (b) N-protecting group, and (c) C 1-6 Alkyl, (d)C 2-6 Alkenyls (e.g., optionally substituted alkyls having one or more double bonds), (e)C 2-6Alkynyl (e.g., optionally substituted alkyl having one or more triple bonds), (f) C 4-18 Aryl, (g) (C 4-18 Aryl)C 1-6 Alkyl (e.g., Lk-Ar, where Lk is the divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl), (h) C 3-8 Cycloalkyl, and, (i) (C 3-8 Cycloalkyl)C 1-6 Alkyl (e.g., -Lk-Cy, where Lk is the divalent form of an optionally substituted alkyl group and Cy is an optionally substituted cycloalkyl as described herein), selected from the group consisting of, and in one embodiment, no two groups are bonded to the nitrogen atom via a carbonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is C 1-3 C 1-6 C 1-12 C 1-16 C 1-18 C 1-20 C 1-24 alkyl group.

[0040] "Alkylene" means the polyvalent (e.g., divalent) form of an alkyl group as described herein. Examples of alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is C 1-3 C 1-6 s C 1-12 C 1-16 C 1-18 C 1-20 C 1-24 C 2-3 C 2-6 C 2-12 C 2-16 C 2-18 C 2-20 C 2-24It is an alkylene group. The alkylene group may be branched or unbranched. Furthermore, the alkylene group may be substituted or unsubstituted. For example, the alkylene group may be substituted with one or more substituents described herein for alkyl groups.

[0041] "Alkinyl" is an optionally substituted C having one or more triple bonds. 2-24 This refers to an alkyl group. The alkynyl group may be cyclic or acyclic, with examples including ethynyl and 1-propynyl. The alkynyl group may also be substituted or unsubstituted. For example, the alkynyl group may be substituted with one or more substituents for alkyl groups as described herein.

[0042] "Alkynylene" is an optionally substituted C having one or more triple bonds. 2-24 This refers to the polyvalent (e.g., divalent) form of an alkyl group, specifically an alkynyl group. Alkynylene groups can be cyclic or acyclic. Alkynylene groups can be substituted or unsubstituted. For example, an alkynylene group may be substituted with one or more substituents described herein for alkyl groups. Non-restrictive examples of alkynylene groups include -C≡C- or -C≡CCH2-.

[0043] "Amide" is -C(O)NR N1 R N2 This means that, here R N1 and R N2 Each of them is independent and is H, or an optionally substituted alkyl, or R N1 and R N2 Each of these, together with the nitrogen atom to which it is bonded, forms a heterocyclyl group as defined herein.

[0044] "Amino" is -NR N1 R N2 This means that, here R N1 and R N2 Each of them is independent and is H, an optionally substituted alkyl, or an optionally substituted aryl, or R N1 and RN2 Each of these, together with the nitrogen atom to which it is bonded, forms a heterocyclyl group as defined herein.

[0045] "Aryl" means any group containing any carbon-based aromatic group, including but not limited to phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, crisenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, etc., such as indanyl, tetrahydronaphthyl, fluorenyl, etc., and condensed benzo-C (as defined herein) 4-8 This includes cycloalkyl radicals. The term aryl also includes heteroaryls, which are defined as groups containing an aromatic group having at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term nonheteroaryl (which is also included in the term aryl) defines groups 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, including any substituents described herein for alkyls.

[0046] "Allylene" refers to the polyvalent (e.g., divalent) form of the aryl group as described herein. Examples of allylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the allylene group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10The allylene group may be branched or unbranched. Furthermore, the allylene group may be substituted or unsubstituted. For example, the allylene group may be substituted with one or more substituents described herein for alkyl or aryl groups.

[0047] "Carbonyl" refers to a -C(O)- group and is sometimes represented as >C=O.

[0048] "Carboxyl" refers to the -CO2H group.

[0049] "Carboxyalkyl" means an alkyl group as defined herein, substituted with one or more carboxyl groups as defined herein.

[0050] "Carboxylaryl" means an aryl group as defined herein, substituted with one or more carboxyl groups as defined herein.

[0051] "Carboxylic acid" means any part or compound containing one or more carboxyl groups. Examples of non-limiting carboxylic acids include carboxyalkyl or carboxyaryl compounds. As used herein, "diacid" refers to a carboxylic acid having two carboxyl groups, and "triacid" refers to a carboxylic acid having three carboxyl groups.

[0052] Unless otherwise specified, "cycloalkenyl" refers to a monounsaturated non-aromatic or aromatic cyclic hydrocarbon group of 3 to 8 carbon atoms having one or more double bonds. Furthermore, the cycloalkenyl group may be substituted or unsubstituted. For example, the cycloalkenyl group may be substituted with one or more substituents, including those described herein for alkyl groups.

[0053] Unless otherwise specified, "cycloalkyl" refers to a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group with 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, cycloheptyl, and bicyclo[2.2.1.]heptyl. Cycloalkyl groups may be substituted or unsubstituted. For example, a cycloalkyl group may be substituted with one or more substituents, including those described herein for alkyl groups.

[0054] "Dicarbonyl" means any part or compound containing two carbonyl groups as defined herein. A non-limiting dicarbonyl part is 1,2-dicarbonyl (e.g., R C1 -C(O)-C(O)R C2 , here, R C1 and R C2 Each of them is independently and optionally substituted with alkyl, halo, optionally substituted with alkoxy, hydroxyl, or leaving group), 1,3-dicarbonyl or 1,3-diketone (e.g., R C1 -C(O)-C(R 1a R 2a )-C(O)R C2 , here, R C1 and R C2 Each of them is independent and can be optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or leaving group, and R 1a and R 2a Each of these is independent of H, or any optional substituent provided for alkyls as defined herein, as well as 1,4-dicarbonyl (e.g., R C1 -C(O)-C(R 1a R 2a )-C(R 3a R 4a )-C(O)R C2 , here, R C1 and R C2 Each of them is independent and can be optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or leaving group, and R 1a , R2a , R 3a , and, R 4a Each of these is independent and comprises H, or an optional substituent provided for alkyls as defined herein.

[0055] "Diol" means a hydroxyalkyl or hydroxyaryl as defined herein, which contains a hydroxyl group.

[0056] "Haro" means F, Cl, Br, or I.

[0057] "Haloalkyl" means an alkyl group as defined herein, substituted with one or more halos.

[0058] "Heteroalkenylene" means the divalent form of an alkenylene group as defined herein, comprising one, two, three, or four non-carbon heteroatoms (e.g., atoms independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halos). Heteroalkenylene groups may be substituted or unsubstituted. For example, a heteroalkenylene group may be substituted with one or more substituents as described herein for alkyl groups. Non-restrictive heteroalkenylene groups include, for example, -NR N1 -Ak-, -Ak-NR N1 -, -O-Ak-, or -Ak-O-, where Ak is an alkenylene optionally substituted as defined herein.

[0059] "Heteroalkylene" means the divalent form of an alkylene group as defined herein, comprising one, two, three, or four non-carbon heteroatoms (e.g., atoms independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halos). Heteroalkylene groups may be substituted or unsubstituted. For example, a heteroalkylene group may be substituted with one or more substituents as described herein for alkyl groups. Non-limiting heteroalkylene groups include, for example, -NR N1 -Ak-, -Ak-NR N1This includes -, -O-Ak-, or -Ak-O-, where Ak is an alkylene optionally substituted as defined herein.

[0060] Unless otherwise specified, "heterocyclyl" refers to a three-, four-, five-, six-, or seven-membered ring (e.g., a five-, six-, or seven-membered ring) containing one, two, three, or four non-carbon heteroatoms (e.g., atoms independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halos). Three-membered rings have 0 to 1 double bonds, four- and five-membered rings have 0 to 2 double bonds, and six- and seven-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocycles is fused to one, two, or three rings independently selected from the group consisting of aryl rings, cyclohexane rings, cyclohexene rings, cyclopentane rings, cyclopentene rings, and other monocyclic heterocycles (e.g., indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl). The heterocycle consists of acridinyl, adenyl, alloxadinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaidazolyl, azaindyl, azesinyl, azepanyl, azepinyl, azetidinyl, azetil, aziridinyl, azilinyl, azokanyl, azosinyl, azonanyl, benzimidazolyl, benzoisothiazolyl, benzoisoxazolyl, benzodiazepinyl, benzodiazosinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxynyl, benzodioxanyl, benzodioxosinyl, benzodioxolyl, benzodithiepinyl, Benzodithinyl, benzodithioxosinyl, benzofuranil, benzophenazinyl, benzopyranonil, benzopyranil, benzopyrenyl, benzopyronil, benzoquinolinil, benzoquinolidinil, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazosinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiadinol, benzothiadinyl, benzothiopyranil, benzothiopyronil, benzotriazepinyl, benzotriazinol, benzotriazinol, benzotriazolyl, benzooxathinyl, benzotrioxepinyl, benzooxadiazepinyl, benzooxathiazepinyl, benzooxathiepinyl,Benzooxathiosinyl, benzoxazepinyl, benzoxazinyl, benzoxazosinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl benzylsultimyl, bipyradinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carborinyl (e.g., β-carborinyl), chromanonyl, chromanil, clomenyl, cinolinil, coumarinil, cytodinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinthionyl, Diaziridinonyl, Diaziridinyl, Diazilinyl, Dibenzoisoquinolinyl, Dibenzoacridinyl, Dibenzocarbazolyl, Dibenzofuranyl, Dibenzophenadinyl, Dibenzopyranonyl, Dibenzopyronyl (xanthonyl), Dibenzoquinoxalinyl, Dibenzothiazepinyl, Dibenzothiepinyl, Dibenzothiophenyl, Dibenzooxepinyl, Dihydroazepinyl, Dihydroazetyl, Dihydrofuranyl, Dihydrofuryl, Dihydroisoquinolinyl, Dihydropyranyl, Dihydropyridinyl, Dihydropyridyl, Dihydroquinolinyl, Dihydro Rothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxyindolyl, dioxyranyl, dioxenyl, dioxynyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, froyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl, Indolinyl, indolidinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranil, isochromanil, isoclomenyl, isoindazoyl, isoindolinyl, isoindolyl, isopyrazolonil, isopyrazolyl, isoxazolidinyl, isoxazolyl, isoquinolinil, isoquinolinil, isothiazolidinyl, isothiazolyl, morpholinil, naphthindazolyl, naphthindolyl, naphthilidinyl, naphthopyranil, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl,Naphthoxindryll, naphthilidinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanil, oxetanonyl, oxetanyl, oxetyl, oxtenail, oxyindryll, oxylanil, oxobenzoisothiazolyl, oxoclomenyl, oxisosoquinolinyl, oxoquinolinyl, oxothiolanil, phenanthrolinyl, phenanthrolinyl, phenadinyl, f Phenothiazinyl, phenothienyl (benzothiofuranil), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, prinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridadinyl, pyridinyl, pyridopyramidinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl) Pyrrolinil, pyrrolizidinil, pyrrolyl (e.g., 2H-pyrrolyl), pyririum, quinazolinil, quinolinil, quinolidinil (e.g., 4H-quinolidinil), quinoxalinil, quinuclidinil, serenadinil, serenazolyl, selenofenyl, succinimidyl, sulforanil, tetrahydrofuranil, tetrahydrofuryl, tetrahydroisoquinolinil, tetrahydroisoquinolyl, tetrahydropyridinil, tetrahydropyridyl (piperidyl), tetrahydropyranil, tetrahydropyronil, tetrahydroquinolinil, tetrahydroquinoli Tetrahydrothienyl, tetrahydrothiophenyl, tetradinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiadinyl), thiadiazolyl, thiantrenyl, thianyl, thianaphthenyl, thiazepinyl, thiadinyl, thiazolidinyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thiethyl, thyranyl, thiokanyl, thiochromanonyl, thiochromanyl, thioclomenyl, thiodiadinyl, thiodiazolyl, thioindoxyl,This includes thiomorpholinyl, thiophenyl, thiopyranil, thiopyronil, thiotriazolyl, thiourazolyl, thiooxanil, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianil, uradinyl, urazolyl, uretidinyl, uretinyl, uricin, uridinyl, xansenyl, xanthinyl, xanthionyl, etc., as well as their variants (e.g., including one or more oxo and / or amino compounds), and their salts. The heterocyclyl group may be substituted or unsubstituted. For example, the heterocyclyl group may be substituted with one or more substituents described herein for alkyl groups.

[0061] "Hydroxamic acid" means a carboxylic acid as defined herein, in which a hydroxyl group is replaced with a hydroxyamino group. Non-limiting hydroxamic acids include R A1 -C(O)NR A2 It contains OH, where R A1 and R A2 Each of these is independent and is H, an optionally substituted alkyl, or an optionally substituted aryl.

[0062] "Hydroxyl" means -OH.

[0063] "Hydroxyalkyl" refers to the alkyl group as defined herein, which is substituted with 1 to 3 hydroxyl groups under the condition that only one hydroxyl group can be attached to one carbon atom of the alkyl group, and examples include hydroxymethyl and dihydroxypropyl.

[0064] "Hydroxyaryl" refers to the aryl group as defined herein, which is substituted with 1 to 3 hydroxyl groups under the condition that only one hydroxyl group can be attached to one carbon atom of the aryl group, with hydroxyphenyl and dihydroxyphenyl being examples.

[0065] "Hydroxycarboxylic acid" means any part or compound having at least one hydroxyl group and at least one carboxyl group.

[0066] A "hydroxyketone" is any part or compound having a carbonyl group and a hydroxyl group as substituents. In certain examples, the carbonyl group can form a ketone or an amide. Non-restrictive hydroxyketones include R A1 -C(O)-R A2 Including, here, R A1 and R A2 Each of these is an optionally substituted alkylene, an optionally substituted alkenylene, an optionally substituted heteroalkylene, or an optionally substituted heteroalkenylene, and R A1 and R A2 At least one of them includes a hydroxyl substituent, R A1 and R A2 Collectively, they form a cyclic group (e.g., a heterocyclyl as defined herein).

[0067] "Hydroxylactone" refers to a cyclic ester having one or more hydroxyl groups. Unrestricted hydroxylactones include R A1 -C(O)-OR A2 This includes, where each of RA1 and RA2 is an optionally substituted alkylene or an optionally substituted alkenylene, and R A1 and R A2 At least one of them includes a hydroxyl substituent, R A1 and R A2 Collectively, they form a cyclic group (e.g., a heterocyclyl as defined herein).

[0068] "Oxo" means an oxygen group.

[0069] As used herein, the terms “top,” “bottom,” “upper side,” “lower side,” “above,” and “below” are used to indicate the relative relationship between structures. The use of these terms does not indicate or require that a particular structure must be placed in a particular location within the apparatus.

[0070] Other features and advantages of the present invention will become apparent from the following description and claims. [Brief explanation of the drawing]

[0071] [Figure 1] A schematic diagram illustrating a non-limiting method for patterning and developing films.

[0072] [Figure 2A] A schematic diagram illustrating a non-limiting method for patterning a film and developing it in the presence of a chelating agent. [Figure 2B] A schematic diagram illustrating a non-limiting method for patterning a film and developing it in the presence of a chelating agent.

[0073] [Figure 3A] A schematic diagram illustrating a non-limited method that utilizes a metal precursor during deposition and a chelating agent during development. [Figure 3B] A schematic diagram illustrating a non-limiting method that utilizes a metal precursor during deposition and a chelating agent during development. (A) A first method 300 for providing either a positive tone resist (path i) or a negative tone resist (path ii) is provided, and (B) a block diagram of a method example 350 is provided.

[0074] [Figure 4] A schematic diagram showing one embodiment of the multi-station processing tool 400.

[0075] [Figure 5] A schematic diagram showing one embodiment of the inductively coupled plasma apparatus 500.

[0076] [Figure 6] A schematic diagram showing one embodiment of the semiconductor processing cluster tool architecture 600. [Modes for carrying out the invention]

[0077] This disclosure generally relates to the field of semiconductor processing. In particular, this disclosure is directed toward the use of one or more metal chelating agents during development. For example, metal chelating agents can selectively remove weakly bound metals (which may be present at the rough interface between the exposed and unexposed PR regions) by strongly binding to metal ions. Thus, such metal chelating agents provide a control knob for manipulating LER / LWR by manipulating the concentration and / or chemical identity of the chelating agent. Although we do not wish to be limited by mechanism, metal chelating agents bind to metals at a rate that depends on the amount of steric hindrance and the physical size of the chelating agent molecule, with the binding to metal ions becoming stronger or weaker depending on the thermodynamic gain resulting from the formation of chemical bonds. As a result, careful selection of the concentration and chemical identity of the chelating agent can provide a control knob for directly manipulating roughness at the interface between the exposed and unexposed regions.

[0078] Without metal chelating agents, optimizing the solvent for wet development balances the LER (Low Exposure Rendering) with optimizing the solubility difference between exposed and unexposed areas. However, using soluble metal chelating agents in wet developers allows for solvents optimized for contrast only in exposed and unexposed areas, while directly addressing the roughness of this interface. The orthogonality between solvent selection and interface improvement by metal chelating agents allows for optimization of developer contrast between exposed and unexposed areas, while also optimizing the LER resulting from roughness at the interface between exposed and unexposed areas, which can be difficult to control without metal chelating agents.

[0079] This specification provides detailed references to specific embodiments of the Disclosure. Examples of specific embodiments are illustrated in the accompanying drawings. While this Disclosure is described in relation to these specific embodiments, it should be understood that it is not intended to limit the Disclosure to such specific embodiments. Rather, it is intended to cover alternatives, variations, and equivalents that may fall within the spirit and scope of this Disclosure. The following description provides numerous specific details to facilitate a full understanding of this Disclosure. This Disclosure can be implemented without some or all of these specific details. Also, detailed descriptions of well-known processing operations have been omitted to avoid unnecessarily obscuring this Disclosure.

[0080] EUV lithography utilizes a patterned EUV resist to form a mask used for etching the underlying layer. The EUV resist may be a polymer-based chemically amplified resist (CAR) produced by liquid-based spin-on technology. Alternatives to CAR are metal oxide-containing films that can be directly photopatterned (such as those from Inpria, Corvallis, Oregon), which are described, for example, in U.S. Patent Publications US2017 / 0102612, US2016 / 0216606, and US2016 / 0116839, and are incorporated herein by reference, at least with respect to their disclosures relating to photopatternable metal oxide-containing films. Such films may be formed by spin-on technology or by dry deposition. Metal oxide-containing films can be patterned directly by EUV exposure in a vacuum atmosphere (i.e., without the use of a separate photoresist), as described, for example, in U.S. Patent No. 9,996,004, issued June 12, 2018, “EUV PHOTOPATTERNING OF VAPOR-DEPOSITED METAL OXIDE-CONTAINING HARDMASKS,” and / or in International Application No. PCT / US19 / 31618, filed May 9, 2019, and published as International Publication No. WO2019 / 217749, to provide a patterning resolution of less than 30 nm. At least their disclosures relating to the composition, deposition, and patterning of directly photopatternable metal oxide films for forming EUV resist masks are incorporated herein by reference. Generally, patterning involves exposing an EUV resist with EUV radiation to form a photopattern on the resist, and then developing it to form a mask by removing a portion of the resist according to the photopattern.

[0081] Directly photopatternable EUV or DUV resists may consist of, or contain, metals and / or metal oxides mixed within an organic component. Metals / metal oxides are highly promising because they can promote EUV or DUV photon adsorption, generate secondary electrons, and / or exhibit high etching selectivity for the underlying film stack and device layers.

[0082] Generally, resists can be used as positive-tone resists or negative-tone resists by controlling the chemical properties of the resist and / or the solubility or reactivity of the developer. Having an EUV resist or DUV resist that can function as either a negative-tone resist or a positive-tone resist is beneficial, and this disclosure includes the use and development of films as either a negative-tone resist or a positive-tone resist.

[0083] Methods using metal chelating agents This disclosure generally includes any useful methods utilizing the metal chelating agents described herein. Such methods may include any useful lithography, vapor deposition, radiation exposure, development, and post-coating treatments described herein.

[0084] The following describes techniques related to EUV processing, but these techniques may also be applicable to other next-generation lithography techniques. Various radiation sources may be used, including EUV (generally around 13.5 nm), DUV (deep UV, generally in the range of 248 nm or 193 nm with an excimer laser source), X-rays (including EUV in the low-energy range of the X-ray region), and e-beams (including a wide energy range).

[0085] Following lithographic exposure to EUV radiation, both EUV-exposed and EUV-unexposed regions are present within the PR film. As shown in Figure 1, an EUV-sensitive film 112 may be placed on the upper surface of a substrate 111. The film 112 may be exposed to EUV radiation 101 to provide an EUV-exposed region 112b and an EUV-unexposed region 112c. In a PR film, radiation exposure may be used to generate activated reaction centers, which can then promote reactions that destabilize or stabilize the film to provide a positive-tone resist or a negative-tone resist, respectively. For example, in a negative-tone metal-containing resist film, the exposed regions may contain EUV-activated reaction centers, which promote crosslinking and stabilization of the film. After development of such a resist, the exposed areas are retained, while the unexposed regions are removed by dissolution of the less stable regions of the film.

[0086] Between these exposed and unexposed regions, there is an interface region where the PR region transitions abruptly from the most exposed region to the completely unexposed region. As can be seen from the figure, the exposed film can be characterized by the presence of an interface region 112a between the exposed / unexposed regions. In such an interface region, the film may provide EUV-exposed reaction centers because it is exposed to EUV. However, it may also provide regions that are completely unreacted or unreacted because the reaction does not proceed to completion.

[0087] Developing such interface regions remains difficult if the developer depends on the completion of such EUV-mediated reactions. As shown in Figure 1, when an exposed film is developed with such a developer 102, the resulting pattern includes not only the exposed region 112b but also the interface region 112a. The presence of the interface region can reduce the fidelity of the pattern in the film and contribute to increased roughness (e.g., increased LER and / or LWR).

[0088] The interface region can be removed by using a metal chelating agent that can target unreacted or partially reacted PR regions. As shown in Figure 2A, a non-limiting method may include exposing a film 212 placed on a substrate to EUV radiation 201 to provide an interface region 212a, an EUV-exposed region 212b, and an EUV-unexposed region 212c. Within the EUV-exposed region 212b, the PR is crosslinked to form metal-oxygen (MO) and metal-oxygen-metal (MOM) bonds and to release ligands from the film. As described herein, such an EUV-exposed region may also include unreacted PR. Within the EUV-unexposed region 212c, the PR retains the initial chemical structure of the metal precursor, where EUV-cleavable unstable ligands are generally retained. Non-limiting EUV-cleavable unstable ligands include any described herein for R in formula (IV) or (V), etc.

[0089] Within the interface region 212a, various chemical species are observed, with metal centers bridging to some extent with the MOM phase, retaining unstable ligands to some extent, and forming M-OH intermediates to some extent. Within this region, weakly bonded metal species can be removed using a metal chelating agent. In some cases, the chelating agent may be selected to preferentially bond to weakly bonded metal species exposed to EUV exposure compared to bonding to EUV-exposed bridging metal species 250. After developing the exposed film 202 with such a chelating agent, the developed film may contain a pattern including the exposed region 212b (Figure 2B).

[0090] In certain cases, a metal chelating agent is a charge-neutral chelating agent that binds metal ions (e.g., with varying bond strengths) while keeping the resulting metal-chelate complex soluble and stable in a developer solvent (e.g., an organic solvent). Thus, a metal chelating agent can be an organically soluble metal chelating agent used in wet developers to form a metal-chelate complex by seeking out and binding weakly bonded metal ions in the interfacial region. If the metal-chelate complex remains soluble in the developer, such a complex can be removed from the wafer when the residue of the wet developer is removed. Non-limiting chelating agents include acetylacetone, formic acid, and derivatives of hydroxypyridinone, as well as others described herein.

[0091] The selection of a chelating agent can depend on any useful chemical and physical properties. In one example, a chelating agent may be selected for its metallic bonding strength, which can be used to adjust how aggressively the interface between exposed and unexposed regions is affected by the presence of the chelating agent. A non-limiting determination of metallic bonding strength may include a stability constant (e.g., logK or logβ) between approximately 5 and approximately 50. In another example, the physical size of the chelating agent (e.g., between approximately 0.1 nm and approximately 10 nm) can be manipulated by adding a polymer backbone, which can be used to adjust which size (e.g., critical dimensions greater than 10 nm) or shape (e.g., flat) features are affected by the use of the metallic chelating agent.

[0092] The presence of metal chelating agents during wet development can provide a further adjustment knob for improving the LER of the developed PR pattern. Using different organically soluble metal chelating agents, a particular organometallic treatment may have an optimized LER by selecting a suitable chelating agent with sufficient bonding strength to remove various types of coarse spots in the PR at the interface between exposed and unexposed areas. Such chelating agent-solvent combinations can be optimized by the chemical type of each compound and the specific concentration of the chelating agent in the solvent or solvent mixture.

[0093] In addition to promoting the removal of metal species, the use of such chelating agents can facilitate the removal of volatile compounds generated by or within the PR film. Non-limited volatile compounds include carbon dioxide, carbon monoxide, alkenes, aromatics, and polyalkyltin species that may be present in the film. Non-limited species include SnR x L y This comprises, where each R is independently and optionally substituted alkyl, and each L is independently a dialkylamino (e.g., -NMe2), hydroxyl, crosslinked oxide, or another ligand, with 4≧x≧1 and 3≧y≧0.

[0094] Thus, volatile compounds that could otherwise release gases and contaminate facilities and equipment can be solubilized as complexes in the solvent. Furthermore, chelating agents may be used to remove sparingly soluble chemical byproducts that may be generated during EUV exposure and deposited on the surface of PR patterned by lithography.

[0095] The removal of interfacial regions and the presence of chelate complexes can be characterized by any useful method. For example, the dissolution of metal centers by chelating agents can be detected by measuring the presence of metal chelate complexes in the developing solution. Non-limiting detection methods include the use of nuclear magnetic resonance (NMR) spectroscopy, liquid chromatography-mass spectrometry (LC-MS), and high-performance liquid chromatography (HPLC).

[0096] Figure 3A provides an example method 300 comprising a step 301 of depositing a film 312 onto the upper surface of a substrate 311. The method may further comprise a step for processing the deposited EUV-sensitive film. Such a step is not necessary for the formation of the film but may be useful when the film is used as PR. Therefore, method 300 further comprises a step of patterning the film by EUV exposure 302 to provide an exposure film having an EUV exposure region 312b and an EUV non-exposure region 312c and an interface region positioned between them. Patterning may involve the use of a mask 314 having an EUV-transmitting region and an EUV-opaque region, where an EUV beam 315 is transmitted to the film 312 through the EUV-transmitting region. EUV exposure may include exposure with wavelengths in the range of about 10 nm to about 20 nm (e.g., about 13.5 nm in a vacuum atmosphere), for example, in a vacuum atmosphere.

[0097] Once a pattern is provided, method 300 may comprise a step 303 of developing in the presence of one or more metal chelating agents, thereby (i) removing the EUV-exposed region to provide a pattern within the positive-tone resist film, or (ii) removing the EUV-unexposed region to provide a pattern within the negative-tone resist. As described herein, an interface region may exist between the EUV-exposed / unexposed regions. Thus, in one embodiment, proceeding to path (i) in Figure 3A, the EUV-exposed region 312B and the interface region are selectively removed, which can be facilitated by using a metal chelating agent to bond to metal species with weaker bonds formed after EUV exposure. Alternatively, proceeding to path (ii) in Figure 3A, the EUV-exposed region 312b and the interface region are retained, which can be facilitated by a metal chelating agent to bond to metal species with weaker bonds present in the EUV-unexposed region compared to metal species present in the EUV-exposed region (e.g., crosslinked metal or crosslinked metal-organic material).

[0098] The development process may involve the use of a liquid-phase aqueous solvent or organic solvent (for example, as a metal chelating agent). Further development conditions are described herein.

[0099] Optional steps may be performed to further adjust, modify, or treat the EUV-sensitive film, substrate, photoresist layer, capping layer, and / or in any manner specified herein. Figure 3B provides a flowchart of Method Example 350 having various operations, including optional operations. As can be seen from the figure, in operation 352, a film is deposited using a metal precursor.

[0100] In an optional operation 354, the back surface or bevel of the substrate may be cleaned and / or edge beads of photoresist deposited in a previous step may be removed. Such cleaning or removal steps may be useful for removing particles that may be present after the deposition of the photoresist layer. The removal steps may include processing the wafer in a wet metal oxide (MeOx) edge bead removal (EBR) step.

[0101] In another example, the method may include an optional operation 356 in which a post-coating bake (PAB) of the deposited photoresist layer is performed, thereby removing residual moisture from the layer to form a film, or pre-treating the photoresist layer in any useful way. The optional PAB may be performed after film deposition and before EUV exposure, and the PAB may include a combination of heat treatment, chemical exposure, and wetting to increase the EUV sensitivity of the film, thereby reducing the EUV dose for developing a pattern in the film. In certain embodiments, the PAB step is performed at a temperature higher than about 100°C, or at a temperature of about 100°C to about 200°C, or at a temperature of about 100°C to about 250°C. In some examples, PAB is not performed in the method. In other examples, the PAB step is performed at a temperature below about 180°C, below about 200°C, or below about 250°C.

[0102] In operation 358, the film is exposed to EUV radiation to develop the pattern. Generally, EUV exposure alters the chemical composition of the film, creating a contrast in etching selectivity that can be used to remove portions of the film. Such contrast can provide a positive-toned resist or a negative-toned resist, as described herein.

[0103] Operation 360 is an optional post-exposure bake (PEB) of the exposed film, thereby further removing residual moisture, promoting chemical concentration within the film, increasing the contrast of the etching selectivity ratio of the exposed film, or post-treating the film in any useful way. Non-limiting examples of PEB temperatures include, for example, about 90°C to 600°C, 100°C to 400°C, 125°C to 300°C, 170°C to 250°C and above, 190°C to 240°C, and other temperatures described herein. In other examples, the PEB process is carried out at temperatures below about 180°C, below about 200°C, or below about 250°C.

[0104] In one example, the exposed film may be thermally treated (e.g., optionally in the presence of various chemical species) to enhance the reactivity of the resist within the EUV-exposed areas when exposed to a release agent (e.g., halogen compound etchants such as HCl, HBr, H2, Cl2, Br2, BCl3, or combinations thereof, aqueous alkaline developers, or organic developers) or a positive-tone developer. In another example, the exposed film may be thermally treated to further crosslink ligands within the EUV-exposed areas of the resist, thereby providing EUV-unexposed areas that can be selectively removed when exposed to a release agent (e.g., a negative-tone developer).

[0105] Next, in operation 362, the PR pattern is developed in the presence of one or more metal chelating agents. In various embodiments of development, exposed areas are removed (positive tone), or unexposed areas are removed (negative tone). In various embodiments, these steps may be wet processes including such metal chelating agents.

[0106] In another example, the method may comprise a step of curing the patterned film (e.g., after development) to provide a resist mask positioned on the upper surface of the substrate. The curing step may include any useful treatments for further crosslinking or reacting the unexposed or exposed areas of the EUV (e.g., exposure to plasma (e.g., plasma of O2, Ar, He, or CO2), exposure to ultraviolet light, annealing (e.g., at temperatures of about 180°C to about 240°C), thermal baking, or a combination of these steps which may be useful for a post-development bake (PDB) step). In other examples, the PDB step is performed at temperatures below about 180°C, below about 200°C, or below about 250°C. Further post-coating treatments are described herein and may be performed as optional steps for any method described herein.

[0107] Any useful type of chemical can be used during the deposition, patterning, stripping, and / or development process. Such process may be based on a dry process using gas-phase chemicals or a wet process using liquid-phase chemicals. For example, spin-on EUV photoresist (wet process), such as that available from Inpria, may be combined with other wet or dry processes described herein. In various embodiments, wafer cleaning may be a wet process described herein. In yet another embodiment, a wet development process may be used in combination with spin-on EUV photoresist or dry-deposited EUV photoresist.

[0108] Metal chelating agents Metal chelating agents may include any ligands that can bond to a metal center (e.g., a transition metal center). Non-restrictive ligands include ligands having a hydroxyl moiety, a carboxyl moiety, an amide moiety, an amino moiety, and / or an oxo moiety. Metal chelating agents may be any useful compound having such ligands, and these compounds may include polymers, dicarbonyls (e.g., diketones), ketones, hydroxyketones (e.g., hydroxypyridinone, hydroxypyrimidone, or hydroxypyrone), alcohols (e.g., diols, triols, etc.), acids (e.g., carboxylic acids, diacides, triacides, hydroxycarboxylic acids, etc.), hydroxy acids (hydroxycarboxylic acids), amides, hydroxyamides, hydroxamic acids, lactones, hydroxylactones (e.g., ascorbic acid), and their substituted forms. Furthermore, other non-limiting metal chelating agents (e.g., wet forms of dry metal chelating agents) may be any chelating agents described in U.S. Provisional Patent Application No. 63 / 199,129, filed December 8, 2020, “PHOTORESIST DEVELOPMENT WITH ORGANIC VAPOR,” which is incorporated herein by reference.

[0109] In other embodiments, the metal chelating agent is a dicarbonyl or comprises a dicarbonyl. Non-limiting dicarbonyls include 1,3-diketones (e.g., R A1 -C(O)-C(R 1a R 2a )-C(O)R A2 Including, here, R A1 and R A2 Each of them is independently an optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkoxy, hydroxyl, optionally substituted aryl, or a leaving group, or optionally R A1 and R A2 Collectively, they form a cyclic group (e.g., an optionally substituted cycloalkyl or an optionally substituted heterocycline), R 1a and R 2aEach of these is independently H, or an optional substituent provided for alkyls as defined herein. Certain dicarbonyls include acetylacetone.

[0110] In some embodiments, the metal chelating agent is an alcohol or contains an alcohol. A non-limiting alcohol is R A1 -OH and R A1 These are optionally substituted alkyls, optionally substituted hydroxyalkyls, optionally substituted hydroxyaryls, optionally substituted carboxyalkyls, optionally substituted carboxyaryls, or optionally substituted aryls. Non-limited alcohols include catechols and glycols.

[0111] In other embodiments, the metal chelating agent is a carboxylic acid or comprises a carboxylic acid. Non-limiting carboxylic acids include R A1 -CO2H, R A1 is H, optionally substituted alkyl, optionally substituted hydroxyalkyl, optionally substituted hydroxyaryl, optionally substituted carboxyalkyl, optionally substituted carboxyaryl, or optionally substituted aryl. Another non-limiting carboxylic acid is HO2C-R Ak -CO2H, R Ak The carboxylic acid is a bond, an optionally substituted alkylene, or an optionally substituted allylene (e.g., optionally substituted with halo, hydroxyl, carboxyl, alkoxy, and / or haloalkyl). In certain embodiments, the carboxylic acid is formic acid, citric acid, or salicylic acid.

[0112] In yet another embodiment, the metal chelating agent is hydroxamic acid (R A1 -C(O)NR A2 OH etc., R A1 and R A2Each of them is independent and is H, an optionally substituted alkyl, or an optionally substituted aryl, or optionally R A1 and R A2 These collectively form heterocyclines that are selectively substituted.

[0113] The metal chelating agent is a hydroxyketone or may contain a hydroxyketone. In certain embodiments, the hydroxyketone is R A1 -C(O)-R A2 And here, R A1 and R A2 Each of these is an optionally substituted alkylene, an optionally substituted alkenylene, an optionally substituted heteroalkylene, or an optionally substituted heteroalkenylene, and R A1 and R A2 At least one of them includes a hydroxy substituent, R A1 and R A2 Collectively, they form cyclic groups (e.g., optionally substituted cycloalkyl or optionally substituted heterocyclyl groups).

[0114] In other embodiments, the hydroxyketone has the structure of the following chemical formulas (I), (II), or (III): [ka] , [ka] [ka] , Alternatively, they may have salts thereof. Here, X1 and X2 are independent and -CR1= or -N=, Each of R1 and R2 is independently H, an optionally substituted alkyl, an optionally substituted hydroxyalkyl, an optionally substituted carboxyalkyl, or -C(O)NRN1 R N2 , or -C(O)OR O1 And here, R N1 , R N2 , and, R O1 Each of them is independent, H ,Ma or is an alkyl group that is optionally substituted, and optionally R N1 and R N2 These collectively form heterocyclines that are selectively substituted. R3 is independent and can be H, an optionally substituted alkyl, or an optionally substituted aryl.

[0115] Non-restrictive hydroxyketones include hydroxypyridinone, hydroxypyrimidone, or hydroxypyrone, and their substituted forms. Further hydroxyketones include 1-hydroxypyridine-2-one (6-R 1 Substitutions such as 1,2-HOPO, 3-hydroxypyridine-4-one (NR 3 Substitutions 3,4-HOPO and NR 3 ,2-R 2 ,6-R 3 Substitutions such as 3,4-HOPO, 3-hydroxypyridine-2-one (NR 3 Substitutions: 3,2-HOPO and 4-R 3 ,6-R 1 Substitutions such as 3,2-HOPO, 1-hydroxypyrazine-2-one (6-R 1 Substitutions include 1,2,4-HPM (such as 1,2,4-HPM), 1-hydroxypyridimin-2-one (6-R 1 Substitutings such as 1,2,3-HPM and 3-hydroxypyran-4-one (2-R 1 Substitutions: 3,4-HPy, 5-R 2 Substitution, and 2-R 1 ,5-R 2 This includes substituted 3,4-HPy (such as 3,4-HPy), where non-limiting substituents are denoted by chemical formula (I), (II), or (III).

[0116] In some embodiments, the metal chelating agent comprises a plurality of parts arranged on a skeleton, where the plurality of parts are selected from hydroxyl, carboxyl, amide, amino, and oxo. Non-limiting parts include one or more of monovalent or polyvalent dicarbonyl, diol, carboxylic acid, diacid, triacid, hydroxycarboxylic acid, hydroxamic acid, hydroxylactone, hydroxyketone, or salts thereof.

[0117] The skeleton may include any useful structure, such as optionally substituted alkyls, optionally substituted heteroalkyls, optionally substituted aryls, and combinations thereof. In other embodiments, the skeleton includes polymers, such as poly(esters), poly(hydroxyalkanoates), poly(lactic acid), poly(vinyl acetate), or copolymers thereof; poly(hydroxyalkanoates); poly(lactic acid); poly(caprolactone); polysaccharides such as amylose, cellulose, carboxymethylcellulose, or derivatives thereof; poly(alkylene succinates), such as poly(propylene succinate) or poly(butylene succinate); poly(aspartate) or poly(aspartic acid); or aliphatic aromatic resins, such as copolymers having at least one aliphatic moiety and at least one aromatic moiety.

[0118] Metal precursors This disclosure relates to the use of metal precursors and optional counter-reactants that can be deposited to form a radiation-sensitive film (e.g., an EUV-sensitive film). This film can then function as an EUV resist, as further described herein. In certain embodiments, the film may contain one or more ligands (e.g., unstable ligands) that can be removed, cleaved, or crosslinked by radiation (e.g., EUV or DUV radiation).

[0119] The metal precursor can include any precursor (e.g., those described herein) that provides a radiation-sensitive, patterning-capable film (or a patterning radiation-sensitive film or a photopatternable film). Such radiation can include EUV radiation, DUV radiation, or UV radiation that becomes patterning radiation by being supplied by irradiation through a patterned mask. The film itself can be modified by being exposed to such radiation so that the film becomes radiation-sensitive. In certain embodiments, the metal precursor is an organometallic compound and includes at least one metal center.

[0120] The metal precursor can have any useful number and type of ligands. In some embodiments, the ligands can be characterized by being able to react in the presence of a counter-reactant or in the presence of patterning radiation. For example, the metal precursor can include ligands (e.g., a dialkylamino group or an alkoxy group) that react with a counter-reactant, whereby a bond (e.g., an -O- bond) between metal centers can be introduced. In another example, the metal precursor can include ligands that desorb in the presence of patterning radiation. Such ligands (EUV-labile ligands) can include a branched or straight-chain alkyl group having a beta hydrogen and others described herein (e.g., R in Chemical Formulas (IV) or (V)).

[0121] The metal precursor can be any useful metal-containing precursor, such as an organometallic agent, a metal halide, or a capping agent (e.g., those described herein). In a non-limiting example, the metal precursor has a structure having the following Chemical Formula (IV): M a R b (IV), where M is a metal or atom having a high EUV absorption cross-section, Each R is independent and can be H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, anionic ligand, neutral ligand, or polydentate ligand. a≧1 and b≧1.

[0122] In another non-limiting example, the metal precursor has a structure having the following chemical formula (V): M a R b L c (V) Here, M is a metal or atom with a high EUV absorption cross-section. Each R is independent and is a halo, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted amino, an optionally substituted alkoxy, or L. Each L is independent and is a ligand, anionic ligand, neutral ligand, polydentate ligand, ion, or other part that reacts with the reactant, where R and L and M collectively and selectively form a heterocyclyl group, or R and L collectively and selectively form a heterocyclyl group. a≧1, b≧1, and c≧1.

[0123] In some embodiments, each ligand in the metal precursor may be a ligand that reacts with the reactant. In one example, the metal precursor has a structure having chemical formula (V), where each R is independent and is L. In another example, the metal precursor has a structure having the following chemical formula (Va): M a L c (Va), Here, M is a metal or atom with a high EUV absorption cross-section. Each L is an independent ligand, ion, or other part that reacts with the reactant, where two Ls can collectively and selectively form a heterocyclyl group. a≧1 and c≧1. In certain embodiments of the chemical formula (Va), a is 1. In further embodiments, c is 2, 3, or 4.

[0124] For any chemical formula in this specification, M is the high patterning radiation absorption cross-section (e.g., 1 x 10⁻¹⁰). 7 cm 2 M may be a metal, metalloid, or atom having an EUV absorption cross-section of 1 / mol or more. In some embodiments, M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), tantalum (Ta), cesium (Cs), indium (In), molybdenum (Mo), hafnium (Hf), iodine (I), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), and platinum (Pt). In further embodiments, in chemical formula (IV), (V), or (Va), M is Sn, a is 1, and c is 4. In other embodiments, in chemical formula (IV), (V), or (Va), M is Sn, a is 1, and c is 2. In certain embodiments, M is Sn(II) (for example, in chemical formulas (IV), (V), or (Va)), thereby providing a metal precursor that is an Sn(II) compound. In other embodiments, M is Sn(IV) (for example, in chemical formulas (IV), (V), or (Va)), thereby providing a metal precursor that is an Sn(IV) compound. In certain embodiments, the precursor contains iodine (for example, in the case of a periodate).

[0125] For any chemical formula in this specification, each R is independently an H group, a halo group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted cycloalkenyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted alkoxy group (e.g., -OR). 1 , here, R 1 The ligands may be optionally substituted alkyl groups, optionally substituted alkanoyloxy groups, optionally substituted aryl groups, optionally substituted amino groups, optionally substituted bis(trialkylsilyl)amino groups, optionally substituted trialkylsilyl groups, oxo groups, anionic ligands (e.g., oxides, chlorides, hydrides, acetates, iminodiaacetates, etc.), neutral ligands, or polydentate ligands.

[0126] In some embodiments, optionally substituted amino acids are -NR 1 R 2 And here, each R 1 and R 2 It is independent and is either an H group or an alkyl group, or R 1 and R 2 Each of these groups, together with the nitrogen atom to which it is bonded, forms a heterocyclyl group as defined herein. In other embodiments, optionally substituted bis(trialkylsilyl)amino groups are -N(SiR 1 R 2 R 3 )2, where each R 1 , R 2 , and, R 3 is an independently and optionally substituted alkyl group. In yet another embodiment, the optionally substituted trialkylsilyl group is -SiR 1 R 2 R 3 And here, each R 1 , R 2 , and, R 3 These are independent, optionally substituted alkyl groups.

[0127] In other embodiments, the chemical formula is -NR 1 R 2 The first R (or first L) and NR 1 R 2 It includes the second R (or second L), where each R 1 and R 2 These are independent and are H or optionally substituted alkyl groups, or R from the first R (or first L). 1 and R from 2R (or 2L) 1 These, together with the nitrogen and metal atoms to which they are each bonded, form a heterocyclyl group as defined herein. In other embodiments, the chemical formula is -OR 1 The first round is -OR 1 It includes the 2nd round, and each round 1 These are independent and are an alkyl group with an H group or an optionally substituted alkyl group, or R from the first R. 1 and R from 2R 1 Together with the oxygen and metal atoms to which each is bonded, these form a heterocyclyl group as defined herein.

[0128] In some embodiments, at least one of R or L (in, for example, chemical formula (IV), (V), or (Va)) is an optionally substituted alkyl group. Non-limiting alkyl groups include, for example, C n H 2n+1 This includes (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl, etc.), where n is 1, 2, 3, or 4 or more. In various embodiments, R or L has at least one beta-hydrogen or beta-fluorine.

[0129] In some embodiments, each R or L (or at least one R or L in chemical formulas (IV), (V), or (Va)) is a halo. In particular, the metal precursor may be a metal halide. Non-limiting metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0130] In some embodiments, each R or L (or at least one R or L in chemical formulas (IV), (V), or (Va)) may contain a nitrogen atom. In certain embodiments, one or more R or L may be optionally substituted aminos, optionally substituted monoalkylaminos (e.g., -NR). 1 H, here, R 1 (where is an optionally substituted alkyl), optionally substituted dialkylamino (e.g., -NR) 1 R 2 Here, each R 1 and R 2 R and L substituents may be independent and optionally substituted alkyl groups, or optionally substituted bis(trialkylsilyl)amino groups. 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.

[0131] In some embodiments, each R or L (or at least one R or L in, for example, chemical formulas (IV), (V), or (Va)) may contain a silicon atom. In certain embodiments, one or more R or L may be optionally substituted trialkylsilyl groups or optionally substituted bis(trialkylsilyl)amino groups. Non-limiting R or L substituents may include, for example, -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2, etc.

[0132] In some embodiments, each R or L (or at least one R or L in, for example, chemical formulas (IV), (V), or (Va)) may contain an oxygen atom. In certain embodiments, one or more R or L may be optionally substituted alkoxys or optionally substituted alkanoyloxys. Non-limiting R or L substituents include, for example, methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), acetate (OC(O)-CH3), and -O=C(CH3)-CH=C(CH3)-O-(acac).

[0133] Any chemical formula in this specification may include one or more neutral ligands. Non-limiting neutral ligands include optionally substituted amines, optionally substituted ethers, optionally substituted alkyls, optionally substituted alkenes, optionally substituted alkynes, optionally substituted benzenes, oxos, or carbon monoxide.

[0134] Any formula in this specification may include one or more polydentate (e.g., bidentate) ligands. Non-limiting polydentate ligands include diketonates (e.g., acetylacetonate (acac) or -OC(R) 1 )-Ak-(R 1 )CO- or -OC(R 1 )-C(R 2 )-(R 1 )CO-), bidentate chelate dinitrogen (for example, -N(R 1 )-Ak-N(R 1 )- or -N(R 3 )-CR 4 -CR 2 =N(R 1 )-), aromatic (e.g., -Ar-), amidinate (e.g., -N(R) 1 )-C(R 2 )-N(R 1 )-), aminoalkoxide (e.g., -N(R 1 )-Ak-O- or -N(R 1 )2-Ak-O-), diazadienyl (for example, -N(R 1 )-C(R2 )-C(R 2 )-N(R 1 )-), cyclopentadienyl, pyrazolate, optionally substituted heterocyclyl, optionally substituted alkylene, or optionally substituted heteroalkylene. In a particular embodiment, each R 1 Each R is independent and is H, an optionally substituted alkyl, an optionally substituted haloalkyl, or an optionally substituted aryl, and each R 2 R is independent and is an alkyl group that is either H or optionally substituted. 3 and R 4 Collectively, these form a heterocycline with arbitrary substitutions, where Ak is an arbitrarily substituted alkylene and Ar is an arbitrarily substituted arylene.

[0135] In certain embodiments, the metal precursor includes tin. In some embodiments, the tin precursor includes SnR, SnR2, SnR4, or R3SnSnR3, where each R is independently H, halo, or optionally substituted C 1-12 Alkyl, optionally substituted C 1-12 Alkoxy, optionally substituted aminos (e.g., -NR) 1 R 2 ), C which is optionally substituted. 2-12 Alkenyl, optionally substituted C 2-12 Alkinyl, optionally substituted C 3-8 Cycloalkyl, optionally substituted aryl, cyclopentadienyl, optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR) 1 R 2 R 3 2) Optionally substituted alkanoyloxy (e.g., acetate), diketonate (e.g., -OC(R) 1 )-Ak-(R 2 )CO-), or bidentate chelate dinitrogen (e.g., -N(R 1 )-Ak-N(R 1)-), and in a particular embodiment, each R 1 , R 2 , and, R 3 They are independent, H or C 1-12 Alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl), where Ak is optionally substituted with C 1-6 These are alkylenes. Non-limiting tin precursors include SnF2, SnH4, SnBr4, SnCl4, SnI4, tetramethyltin (SnMe4), tetraethyltin (SnEt4), trimethyltin chloride (SnMe3Cl), dimethyltin dichloride (SnMe2Cl2), methyltin trichloride (SnMeCl3), tetraalyltin, tetravinyltin, hexaphenyltin(IV) (Ph3Sn-SnPh3, where Ph is phenyl), and di Butyldiphenyltin (SnBu2Ph2), trimethyl(phenyl)tin (SnMe3Ph), trimethyl(phenylethynyl)tin, tricyclohexyl tin hydride, tributyltin hydride (SnBu3H), dibutyltin diacetate (SnBu2(CH3COO)2), tin(II) acetylacetonate (Sn(acacac)2), SnBu3(OEt), SnBu2(OMe)2, SnBu3(OMe), Sn( t-BuO)4, Sn(n-Bu)(t-BuO)3, tetrakis(dimethylamino)tin(Sn(NMe2)4), tetrakis(ethylmethylamino)tin(Sn(NMeEt)4), tetrakis(diethylamino)tin(IV)(Sn(NEt2)4), (dimethylamino)trimethyltin(IV)(Sn(Me)3(NMe2), Sn(i-Pr)(NMe2)3, Sn(n-Bu)(NMe2)3, Sn(s-Bu)(NM Includes e2)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-diazastannolysin-2-ylidene), or bis[bis(trimethylsilyl)amino]tin(Sn[N(SiMe3)2]2).

[0136] In other embodiments, the metal precursor includes bismuth (such as in BiR3), where each R is independently and optionally substituted with a halo. 1-12 Alkyl, Mono-C 1-12 Alkylamino (e.g., -NR) 1 H), G-C 1-12 Alkylamino (e.g., -NR) 1 R 2 ), optionally substituted aryl, optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR 1 R 2 R 3 )2) or diketonates (e.g., -OC(R 4 )-Ak-(R 5 )CO-), which is. In a particular embodiment, each R 1 , R 2 , and, R 3 It is independent, C 1-12 Alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl), and each R 4 and R 5 These are independent and can be replaced by H or optionally C. 1-12 The alkyl group is (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl). Non-limiting 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-heptanedione.

[0137] In other embodiments, the metal precursor comprises tellurium (such as TeR2 or TeR4), where each R is independently a halo, C 1-12 Alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl), optionally substituted C 1-12It is alkoxy, optionally substituted aryl, hydroxyl, oxo, or optionally substituted trialkylsilyl. Non-limiting tellurium precursors include dimethyltellurium (TeMe2), diethyltellurium (TeEt2), di(n-butyl)tellurium (Te(n-Bu)2), di(isopropyl)tellurium (Te(i-Pr)2), di(t-butyl)tellurium (Te(t-Bu)2), t-butyltellurium hydride (Te(t-Bu)(H)), Te(OEt)4, bis(trimethylsilyl)tellurium (Te(SiMe3)2), and bis(triethylsilyl)tellurium (Te(SiEt3)2).

[0138] The metal precursor may contain cesium. Non-limiting cesium precursors include Cs(OR), where R is optionally substituted C 1-12 alkyl or optionally substituted aryl. Other cesium precursors include Cs(Ot-Bu) and Cs(Oi-Pr).

[0139] The metal precursor may contain antimony (such as in SbR3), where each R is independently halo, optionally substituted C 1-12 alkyl (such as methyl, ethyl, isopropyl, t-butyl, and neopentyl), optionally substituted C 1-12 alkoxy, or optionally substituted amino (such as -NR 1 R 2 where each R 1 and R 2 are independently H or optionally substituted C 1-12 alkyl). Non-limiting antimony precursors include SbCl3, Sb(OEt)3, Sb(On-Bu)3, and Sb(NMe2)3.

[0140] Other metal precursors include indium precursors (such as in InR3), where each R is independently halo, optionally substituted C 1-12Alkyl compounds (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), or diketonates (e.g., -OC(R) 4 )-Ak-(R 5 )CO-, here each R 4 and R 5 They are independent, H or C 1-12 (It is alkyl). Non-restrictive indium precursors include InCp, where Cp is cyclopentazinyl, InCl3, InMe3, In(acac)3, In(CF3COCHCOCH3)3, and In(thd)3.

[0141] Furthermore, other metal precursors include molybdenum precursors (MoR4, MoR5, MoR6, etc.), where each R is independently and optionally substituted with C. 1-12 Alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), optionally substituted allyl (e.g., allyl such as C3H5, or oxides of allyl such as C5H5O), optionally substituted alkylimides (e.g., =NR) 1 ), acetonitrile, optionally substituted amino acids (e.g., -NR) 1 R 2 ), halo (e.g., chloro or bromo), carbonyl, diketonate (e.g., OC(R) 3 )-Ak-(R 3 )CO-), or bidentate chelate dinitrogen (for example, N(R 3 )-Ak-N(R 3 )- or -N(R 4 )-CR 5 -CR 2 =N(R 3 )-), including. In a particular embodiment, each R 1 and each R 2 Each R is independent and is an alkyl group that is either H or optionally substituted, and each R 3 R is independent and is H, an optionally substituted alkyl, an optionally substituted haloalkyl, or an optionally substituted aryl, 4 and R 5These collectively form heterocyclines that are optionally substituted. Non-restrictive molybdenum precursors include Mo(CO)6, bis(t-butylimide)bis(dimethylamino)molybdenum(VI) i.e., Mo(NMe2)2(=NT-Bu)2, molybdenum(VI) dioxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate) i.e., Mo(=O)2(thd)2, or molybdenum allyl complexes (Mo(η 3 -Allyl)X(CO)2(CH3CN)2, etc., where allyl can be C3H5 or C5H5O, and X can be Cl, Br, or alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl).

[0142] The metal precursor may include hafnium precursors (such as HfR3 and HfR4), where each R is independently and optionally substituted with C. 1-12 Alkyl, optionally substituted C 1-12 Alkoxy, Mono-C 1-12 Alkylamino (for example, NR) 1 H, here, R 1 This is C, which is optionally substituted. 1-12 Alkyl), di-C 1-12 Alkylamino (for example, NR) 1 R 2 , each R 1 and R 2 These are independent and optionally substituted C 1-12 Alkyl), optionally substituted aryl (e.g., phenyl, benzene, or cyclopentadienyl, and their substituted forms), optionally substituted allyl (e.g., allyl or allyl oxide), or diketonates (e.g., OC(R) 4 )-Ak-(R 5 )CO-, each R 4 and R 5 These are independent and can be replaced by H or optionally C. 1-12 Alkyl) is a non-limiting hafnium precursor. HF(I-Pr)(NMe2)3, HF(η-C6H5R 1 )(η-C3H5)2(R1 (H or alkyl), HfR 1 (NR 2 R 3 )3(Here, R 1 , R 2 , and, R 3 Each of them is independent and can be optionally substituted with C. 1-12 This includes alkyl groups (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl), HfCp2Me2, Hf(Ot-Bu)4, Hf(OEt)4; Hf(NEt2)4, Hf(NMe2)4; Hf(NMeEt)4, and Hf(thd)4.

[0143] Further metal precursors and non-limiting substituents are described herein. For example, the metal precursor may be any precursor having the structures of chemical formulas (IV), (V), and (Va) as described above, or any precursor having the structures of formulas (VI), (VII), (VIII), (IX), (X), or (XI), as described later. Any substituent among the substituents M, R, X, or L described herein may be used in any of the chemical formulas (IV), (V), (Va), (VI), (VII), (VIII), (IX), (X), or (XI).

[0144] Various atoms present in the metal precursor and / or reactant can be provided within the gradient film. In some embodiments of the techniques discussed herein, a non-limiting strategy that can further improve the EUV sensitivity in photoresist (PR) films is a strategy that produces films in which the film composition gradually changes vertically, resulting in depth-dependent EUV sensitivity. In homogeneous PRs with high absorption coefficients, the light intensity decreases with increasing depth, requiring higher EUV doses to ensure that the bottom is sufficiently exposed. By increasing the density of atoms with higher EUV absorptivity at the bottom of the film than at the top (i.e., by creating a gradient with increasing EUV absorptivity), it becomes possible to more efficiently utilize available EUV photons while more uniformly distributing absorption (and secondary electron effects) toward the more absorbent bottom of the film. In one non-limiting example, the gradient film contains Te, I, or other atoms toward the bottom of the film (e.g., toward the substrate).

[0145] Strategies for designing vertical compositional gradients within PR films are particularly applicable to dry deposition methods (MLD, CVD, and ALD, etc.) and can be achieved by adjusting the flow ratios between different reactants during deposition. Types of compositional gradients that can be designed include ratios between different high-absorption metals, proportions of metal atoms with EUV-cleavable organic groups, proportions of reactants containing high-absorption elements, and combinations of the above.

[0146] Furthermore, compositional gradients in EUV PR films can offer additional advantages. For example, high-density, highly EUV-absorbing elements at the bottom of the film can effectively generate more secondary electrons, allowing for better exposure of the upper portion of the film. Moreover, such compositional gradients can be directly correlated with a higher proportion of EUV-absorbing species not bound to bulky terminal substituents. For instance, in the case of Sn-based resists, it is possible to incorporate a tin precursor with four leaving groups, thereby promoting the formation of Sn-O-substrate bonds at the interface for improved adhesion.

[0147] Such gradient films can be formed using any metal precursor (e.g., tin precursor or non-tin precursor) and / or reactant described herein. Furthermore, other films, methods, precursors, and other compounds are described in U.S. Provisional Patent Application No. 62 / 909,430 filed on October 2, 2019, and International Publication No. WO2021 / 067632, International Application PCT / US20 / 53856, “SUBSTRATE SURFACE MODIFICATION WITH HIGH EUV ABSORBERS FOR HIGH PERFORMANCE EUV PHOTORESISTS,” filed on October 1, 2020, and International Publication No. WO2020 / 264557, International Application PCT / US20 / 70172, “PHOTORESIST WITH MULTIPLE PATTERNING RADIATION-ABSORBING ELEMENTS AND / OR VERTICAL COMPOSITION,” filed on June 24, 2020. Disclosures relating to the composition, deposition, and patterning of metal oxide films that can be directly photopatterned for forming EUV resist masks, as described in "GRADIENT," are incorporated herein by reference.

[0148] Furthermore, two or more different precursors may be used within each layer (e.g., film). For example, two or more of the metal-containing precursors of this specification may be used to form an alloy. In one non-limiting example, tin telluride may be formed using a tin precursor containing an -NR2 ligand together with an RTeH, RTed, or TeR2 precursor, where R is alkyl (particularly t-butyl or i-propyl). In another example, a metal telluride may be formed using a first metal precursor containing an alkoxy or halo ligand (e.g., SbCl3) together with a tellurium-containing precursor containing a trialkylsilyl ligand (e.g., bis(trimethylsilyl)tellurium).

[0149] Further examples of EUV-sensitive materials, as well as processing methods and apparatus, are described in U.S. Patent No. 9,996,004 and International Patent Publication No. WO2019 / 217749, respectively, which are incorporated herein by reference in their entirety.

[0150] As described herein, the films, layers, and methods herein may be used with any useful precursor. In some examples, the metal precursor includes a metal halide having the following chemical formula (VI): MX n (VI), Here, M is a metal, X is a halide, and n is 2 to 4 depending on the choice of M. Examples of metals M include Sn, Te, Bi, or Sb. Examples of metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0151] Another non-limiting metal precursor has a structure with chemical formula (VII): MR n (VII) Here, M is a metal, each R is independently H, optionally substituted alkyl, amino (e.g., -NR2, where each R is independently alkyl), optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR3)2, where each R is independently alkyl), or optionally substituted trialkylsilyl (e.g., -SiR3, where each R is independently alkyl), and n is 2 to 4 depending on the choice of M. Examples of metals for M include Sn, Te, Bi, or Sb. Alkyl groups are C n H 2n+1This may be the case, where n is 1, 2, 3, or 4 or more. Examples of organometallic agents include SnMe4, SnEt4, TeRn, RTeR, t-butyl telluride (Te(t-Bu)(H)), dimethyl telluride (TeMe2), di(t-butyl) telluride (Te(t-Bu)2)), di(isopropyl) telluride (Te(i-Pr)2), bis(trimethylsilyl) telluride (Te(SiMe3)2), bis(triethylsilyl) telluride (Te(SiEt3)2), tris(bis(trimethylsilyl)amide) bismuth (Bi[N(SiMe3)2]3), Sb(NMe2)3, etc.

[0152] Another non-limiting metal-containing precursor may include a capping agent having the following chemical formula (VIII): ML n (VIII) Here, M is a metal, and each L is independently and optionally substituted alkyl, amino (e.g., -NR). 1 R 2 , here, R 1 and R 2 Each of these may be H or alkyl (such as any as specified herein), alkoxy (e.g., -OR, where R is alkyl (such as any as specified herein)), halo, or other organic substituent, where n is 2 to 4 depending on the choice of M. Examples of metals for M include Sn, Te, Bi, or Sb. Examples of ligands include dialkylamino (e.g., dimethylamino, methylethylamino, and diethylamino), alkoxy (e.g., t-butoxy and isopropoxy), halo (e.g., F, Cl, Br, and I), or other organic substituents (e.g., acetylacetone or N 2 ,N 3 It includes (-di-tert-butyl-butane-2,3-diamino). Non-limiting capping agents include SnCl4, SnI4, Sn(NR2)4 (where each of R is independently methyl or ethyl), or Sn(t-BuO)4. In some embodiments, multiple types of ligands exist.

[0153] The metal-containing precursor may include a hydrocarbyl-substituted capping agent having the following chemical formula (IX): R n MX m (IX), Here, M is a metal, and R is C 2-10 R is an alkyl group or a substituted alkyl group having a beta hydrogen, and X is a suitable leaving group for reaction with the hydroxyl group in the exposed hydroxyl group. In various embodiments, n=1 to 3 and m=4-n, 3-n, or 2-n (where m>0 (i.e., m≧1)). For example, R may be t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n-pentyl, n-hexyl, or derivatives thereof having a heteroatom substituent at the beta position. Suitable heteroatoms include halogens (F, Cl, Br, or I) or oxygen (-OH or OR). X may be a dialkylamino (e.g., dimethylamino, methylethylamino, or diethylamino), an alkoxy (e.g., t-butoxy, isopropoxy), a halo (e.g., F, Cl, Br, or I), or another organic ligand. Examples of hydrocarbyl substitution capping agents include t-butyltris(dimethylamino)tin (Sn(t-Bu)(NMe2)3), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe2)3), t-butyltris(diethylamino)tin (Sn(t-Bu)(NEt2)3), di(t-butyl)di(dimethylamino)tin (Sn(t-Bu)2(NMe2)2), sec-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe2)3), and n-pentyltris(dimethyl This includes triaminotin (Sn(n-pentyl)(NMe2)3), i-butyltris(dimethylamino)tin (Sn(i-Bu)(NMe2)3), i-propyltris(dimethylamino)tin (Sn(i-Pr)(NMe2)3), t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO)3), n-butyl(tris(t-butoxy)tin (Sn(n-Bu)(t-BuO)3), or isopropyltris(t-butoxy)tin (Sn(i-Pr)(t-BuO)3).

[0154] In various embodiments, the metal-containing precursor contains at least one alkyl group on each metal atom that may remain after the gas-phase reaction, while other ligands or ions coordinated to the metal atoms may be substituted by the reactant. Thus, another non-limiting metal-containing precursor comprises an organometallic agent having chemical formula (X): M a R b L c (X), Here, M is a metal, R is an optionally substituted alkyl, and L is a ligand, ion, or other part that reacts with the reactant, with a≧1, b≧1, and c≧1. In certain embodiments, a=1 and b+c=4. In some embodiments, M is Sn, Te, Bi, or Sb. In certain embodiments, each L is independently an amino (e.g., -NR). 1 R 2 , here, R 1 and R 2 Each of these may be H or alkyl (such as any as described herein), alkoxyl (e.g., -OR, where R may be alkyl (such as any as described herein)), or halo (e.g., F, Cl, Br, or I). Examples of organometallic agents include SnMe3Cl, SnMe2Cl2, SnMeCl3, SnMe(NMe2)3, SnMe2(NMe2)2, SnMe3(NMe2), and the like.

[0155] In other embodiments, the non-limiting metal-containing precursor includes an organometallic agent having chemical formula (XI): M a L c (XI), Here, M is a metal, and L is a ligand, ion, or other part that reacts with the reactant, with a≧1 and c≧1. In certain embodiments, c=n-1, where n is 2, 3, or 4. In some embodiments, M is Sn, Te, Bi, or Sb. The reactant is preferably replaceable with a reactive part, ligand, or ion (e.g., L in the chemical formulas herein) to chemically bond at least two metal atoms.

[0156] In any embodiment of this specification, R is an optionally substituted alkyl (e.g., C 1-10 It may be alkyl. In one embodiment, the alkyl is substituted with one or more halos (e.g., halo-substituted C containing 1, 2, 3, 4, or 5 or more halos (F, Cl, Br, or I, etc.)). 1-10 (Alkyl). An example of an R substituent is C n H 2n+1 (where n≧3 is preferable), and C n F x H (2n+1-x) (where 2n+1≦x≦1) is included. In various embodiments, R has at least one beta-hydrogen or beta-fluorine. For example, R may be selected from the group consisting of i-propyl, n-propyl, t-butyl, i-butyl, n-butyl, sec-butyl, n-pentyl, i-pentyl, t-pentyl, sec-pentyl, and mixtures thereof.

[0157] In any embodiment of this specification, L is an amino acid (e.g., -NR) 1 R 2 , R 1 and R 2Each of these may be any part that is readily substituted by the reactant to form the M-OH moiety, such as a part selected from the group consisting of H or alkyl (such as any as described herein), alkoxy (e.g., -OR, where R is alkyl (such as any as described herein)), carboxylate, halo (e.g., F, Cl, Br, or I), and mixtures thereof.

[0158] Examples of organometallic compounds include SnMeCl3, (N 2 ,N 3 -di-t-butylbutan-2,3-diamide)tin(II)(Sn(tbba)), bis(bis(trimethylsilyl)amide)tin(II), tetrakis(dimethylamino)tin(IV)(Sn(NMe2)4), t-butyltris(dimethylamino)tin(Sn(t-butyl)(NMe2)3), i-butyltris(dimethylamino)tin(Sn(i-Bu)(NMe2)3), n-butyltris(dimethylamino)tin(Sn(n-Bu) This includes (NMe2)3), sec-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe2)3), i-propyl(tris)dimethylaminotin (Sn(i-Pr)(NMe2)3), n-propyltris(diethylamino)tin (Sn(n-Pr)(NEt2)3), and similar alkyl(tris)(t-butoxy)tin compounds (such as t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO)3)). In some embodiments, the organometallic agents are partially fluorinated.

[0159] Lithography EUV lithography utilizes EUV resists, which may be polymer-based chemically amplified resists produced by liquid-based spin-on techniques, metal oxide-based resists produced by spin-on techniques, or metal oxide-based resists produced by dry deposition techniques. Such EUV resists may include any EUV-sensitive films or materials described herein. A lithography method may include, for example, the steps of patterning the resist by exposing it to EUV radiation to form a photopattern, and then developing the pattern by removing a portion of the resist according to the photopattern to form a mask.

[0160] Furthermore, while this disclosure relates to lithography patterning techniques and materials, exemplified by EUV lithography, it should be understood that it is also applicable to other next-generation lithography techniques. In addition to EUV, including the standard 13.5 nm EUV wavelength currently in use and under development, the most suitable radiation sources for such lithography are DUV (deep UV) (generally referring to the use of 248 nm or 193 nm excimer laser sources), X-rays (formally including EUV in the relatively low energy range of the X-ray range), and e-beams (which can cover a wide energy range). Such methods include contacting a substrate (e.g., having optionally exposed hydroxyl groups) with a metal-containing precursor (e.g., any precursor described herein) to form a film of metal oxide (e.g., a layer containing a network of metal oxide bonds, which may also contain other nonmetallic 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 method described in this application is merely an example of methods and materials that may be available in the current art.

[0161] The directly photopatternable EUV resist may consist of, or contain, metals and / or metal oxides mixed within an organic component. Metals / metal oxides are very promising because they can promote EUV photon adsorption, generate secondary electrons, and / or exhibit high etching selectivity for the underlying film stack and device layers. A wet (solvent) approach is also included in this disclosure. In wet development, the wafer may be exposed to a developing solvent, dried, and baked.

[0162] Deposition treatment such as dry deposition or wet deposition As described above, this disclosure provides a method for forming an imaging layer on a semiconductor substrate that can be patterned using EUV or other next-generation lithography techniques. The method includes a method in which a polymerized organometallic material is generated in vapor or solvent and deposited onto the substrate. In some embodiments, the deposition can utilize any useful metal-containing precursor (e.g., metal halides, capping agents, or organometallic agents described herein) as a dry compound or spin-on compound. The deposition process may include a step of coating the EUV-sensitive material as a resist film. Examples of EUV-sensitive materials are described herein.

[0163] This technology includes a method for depositing an EUV-sensitive film onto a substrate, the film of which can function as a resist for subsequent EUV lithography and processing.

[0164] Such EUV-sensitive films contain materials that, upon exposure to EUV, undergo changes such as the loss of bulky pendant ligands bonded to metal atoms within a low-density M-OH-rich material, enabling crosslinking to a denser MOM-bonded metal oxide material. In other embodiments, EUV exposure provides a denser MLM-bonded organometallic material by resulting in further crosslinking between ligands bonded to metal atoms, where L is a ligand. In yet another embodiment, EUV exposure results in ligand loss to provide an M-OH material that can be removed by a positive-tone developer.

[0165] EUV patterning creates regions of the film with altered physical or chemical properties compared to unexposed areas. These properties can be utilized in subsequent processes, such as to dissolve either the unexposed or exposed regions, or to selectively deposit material onto either the exposed or unexposed regions. In some embodiments, the unexposed film has a hydrophobic surface, and the exposed film has a hydrophilic surface under conditions under which such subsequent processes are performed (the hydrophilicity of the exposed and unexposed regions is recognized as relative to each other). For example, material removal may be performed by utilizing differences in the chemical composition, density, and crosslinking of the film. Removal may be by wet processing, as further described herein.

[0166] The thickness of the EUV patternable film formed on the surface of the substrate can vary depending on the surface features, the materials used, and the processing conditions. In various embodiments, the film thickness may be in the range of about 0.5 nm to about 100 nm. Preferably, the film is thick enough to absorb most of the EUV light under EUV patterning conditions. For example, the total absorption rate of the resist film may be 30% or less (e.g., 10% or less or 5% or less) so that the resist material at the bottom of the resist film is sufficiently exposed. In some embodiments, the film thickness is 10 nm to 20 nm. Furthermore, as described above, since the deposited film can closely match surface features, it offers advantages when forming a mask on a substrate (such as a substrate with underlying features) without "filling" or otherwise planarizing such features.

[0167] The film (e.g., an imaging layer) may consist of a metal oxide layer deposited by any useful method. Such a metal oxide layer may be deposited or coated using any EUV-sensitive material described herein, such as a metal-containing precursor (e.g., a metal halide, a capping agent, or an organometallic agent). In an example process, a polymerized organometallic material is formed in the gas phase, in the liquid phase, or in situ on the surface of a substrate to provide a metal oxide layer. The metal oxide layer may be used as a film, an adhesive layer, or a capping layer.

[0168] Optionally, the metal oxide layer may include a hydroxyl-terminated metal oxide layer, which can be deposited by utilizing a capping agent (e.g., any of those described herein) together with an oxygen-containing reactant. Such a hydroxyl-terminated metal oxide layer can be used as an adhesive layer between two other layers, for example, between a substrate and a film and / or between a photoresist layer and a lower layer.

[0169] Examples of deposition techniques (for films, for example) include ALD (e.g., thermal ALD and plasma-enhanced ALD), PVD such as spin-coat deposition and PVD-coated sputtering, CVD (e.g., PE-CVD or LP-CVD), sputter deposition, electron beam deposition including electron beam-coated deposition, or any combination thereof (such as a combination of ALD and CVD components, or discontinuous ALD processes where metal-containing precursors and their reactants are separated in time or space).

[0170] Further descriptions of precursors applicable to this disclosure and methods for depositing them as EUV photoresist films can be found in International Application PCT / US19 / 31618, “METHODS FOR MAKING EUV PATTERNABLE HARD MASKS,” filed on 9 May 2019 and published as International Publication WO2019 / 217749. The thin films may contain optional materials in addition to the metal precursors and reactants to alter the chemical or physical properties of the film, such as changing the film’s sensitivity to EUV or increasing its etching resistance. Such optional materials may be introduced by doping before deposition on the substrate, after deposition of the film, or both. In some embodiments, a mild, distant H2 plasma may be introduced, for example, to replace some Sn-L bonds with Sn-H, thereby increasing the reactivity of the resist under EUV.

[0171] Dry deposition methods may comprise the steps of: mixing a vapor stream of a metal precursor (e.g., a metal-containing precursor such as an organometallic agent) with a vapor stream of an optional reactant; and depositing the organometallic material onto the surface of a semiconductor substrate. In some embodiments, the polymerized organometallic material can be formed by mixing the metal-containing precursor with an optional reactant. As will be understood by those skilled in the art, the mixing and deposition aspects of the process may be carried out in parallel in a substantially continuous process. Wet deposition methods may comprise the step of providing the precursor or polymerized organometallic material in a liquid solvent.

[0172] In an example of continuous CVD processing, two or more gas streams of a metal precursor and an optional reactant are introduced into the deposition chamber of the CVD apparatus through separate inlets, where the gases mix and react in the gas phase to form an aggregated polymer material or film on the substrate (e.g., by the formation of metal-oxygen-metal bonds). The gas streams may be introduced, for example, using separate inlets or a dual plenum showerhead. The apparatus is configured such that the streams of the metal precursor and the optional reactant are mixed in the chamber, allowing the metal precursor and the optional reactant to react and form a polymerized organometallic material or film (e.g., a metal oxide coating or aggregated polymer material by the formation of metal-oxygen-metal bonds).

[0173] To deposit metal oxides, the CVD process is generally carried out under reduced pressure, such as 0.1 Torr to 10 Torr. In some embodiments, the process is carried out at a pressure of 1 Torr to 2 Torr. The substrate temperature is preferably lower than the reaction fluid temperature. For example, the substrate temperature may be 0°C to 250°C, or ambient temperature (e.g., 23°C) to 150°C.

[0174] To deposit aggregated polymer materials, CVD treatment is generally carried out under reduced pressure, such as 10 mTorr to 10 Torr. In some embodiments, the treatment is carried out at 0.5 to 2 Torr. The substrate temperature is preferably below the temperature of the reaction fluid. For example, the substrate temperature may be 0°C to 250°C, or ambient temperature (e.g., 23°C) to 150°C. In various treatments, the deposition of polymerized organometallic materials onto the substrate occurs at a rate inversely proportional to the surface temperature. Without limiting the mechanism, function, or usefulness of this technology, the products of such gas-phase reactions are thought to have a large molecular weight because the metal atoms are cross-linked with their reactants before condensing or otherwise depositing onto the substrate.

[0175] Vapor deposition methods may be used to adjust the composition of the film as it grows. In CVD processes, this may be achieved by changing the relative flow rates of the metal precursor and the reactant during deposition. Vapor deposition can occur at temperatures from 30°C to 200°C and pressures from 0.01 Torr to 100 Torr (more commonly, about 0.1 Torr to 10 Torr).

[0176] Furthermore, a film (e.g., a metal oxide coating or agglomerated polymer material, such as by the formation of metal-oxygen-metal bonds) may be deposited by ALD treatment. For example, a metal precursor and an optional reactant are introduced at separate times representing the ALD cycle. The metal precursor reacts on the surface, forming up to a monolayer of the material at a time during each cycle. This allows for excellent control of the uniformity of the film thickness on the surface. ALD treatment is generally performed under reduced pressure, such as 0.1 Torr to 10 Torr. In some embodiments, the treatment is performed at 1 Torr to 2 Torr. The substrate temperature may be 0°C to 250°C, or ambient temperature (e.g., 23°C) to 150°C. The treatment may be a heat treatment, or preferably plasma-assisted deposition.

[0177] Any of the deposition methods described herein can be modified to allow the use of two or more different metal precursors. In one embodiment, the precursors may contain the same metal but different ligands. In another embodiment, the precursors may contain different metal groups. In one non-limiting example, alternating flows of various volatile metal-containing precursors can provide a mixed metal layer, such as using a metal alkoxide precursor having a first metal (e.g., Sn) together with a silyl precursor having a different second metal (e.g., Te). Furthermore, any of the deposition methods described herein can be modified to allow the use of two or more different reactants.

[0178] Furthermore, any of the deposition methods described herein can be modified to provide one or more layers within the film. In one example, different metal precursors may be used in each layer. In another example, the same precursor may be used in each layer, but the top layer may have a different chemical composition (e.g., different densities of metal ligand bonding, different metal-to-carbon ratios, or different ligands, provided by adjusting or altering the metal precursor).

[0179] The processes described herein are available for achieving surface modification. A vapor of a metal precursor may be passed over a wafer in several iterations. The wafer may be heated to provide thermal energy for the reaction to proceed. During the several iterations, the heating may be between approximately 50°C and approximately 250°C. In some examples, pulses of the reactant may be utilized and separated by pumping and / or purging steps. For example, the reactant may be pulsed between precursor pulses to induce ALD or ALD-like growth. In other cases, both the precursor and the reactant may be passed through simultaneously. Examples of elements useful for surface modification include I, F, Sn, Bi, Sb, Te, and oxides or alloys of these compounds.

[0180] The processes described herein can be used to deposit thin metal oxides or metals. Examples include SnOx, BiOx, and Te, etc. After deposition, the film is prepared as described elsewhere in this specification. a R b L c The substrate may be capped with an alkyl-substituted precursor in the form of [formula]. A counterpart reactant may be used to better remove the ligand, and multiple cycles may be repeated to ensure complete saturation of the substrate surface. The surface can then be prepared for the deposition of an EUV-sensitive film. One possible method is to produce a thin film of SnOx. Possible chemical reactions include the growth of SnO2 by cycling tetrakis(dimethylamino)tin and a counterpart reactant (such as water or O2 plasma). After growth, a capping agent may be used. For example, isopropyltris(dimethylamino)tin vapor may be flowed over the surface.

[0181] The deposition process is applicable to any useful surface. As used herein, “surface” refers to a surface on which the film of the Technology is deposited or exposed to EUV during the process. Such a surface may be located on a substrate (e.g., on which the film is deposited), on a film (e.g., on which a capping layer may be deposited), or on an underlying layer.

[0182] Any useful substrate may be used, including any material configuration suitable for lithography, particularly for the manufacture 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 ("underlying topographic features") are formed and which has an irregular surface topography.

[0183] Such underlying topographic features may include areas where material has been removed (e.g., by etching) or added (e.g., by vapor deposition) during processing before the method of this technique is implemented. Such pretreatment may include the method of this technique or other processing methods in an iterative process in which two or more feature layers are formed on a substrate. Various advantages can be obtained from the ability to match the film of this technique to the underlying features without "filling" or otherwise planarizing such features, and from the ability to vapor-deposit the film onto various material surfaces.

[0184] In some embodiments, the input wafer may be prepared to have a substrate surface of a desired material, where the top layer is the layer onto which the resist pattern is transferred. The choice of material may vary depending on the integration, but generally, it is desirable to select a material that can be etched with a high selectivity ratio (i.e., much faster) to the EUV resist or imaging layer. Suitable substrate materials include various carbon-based films (e.g., ashable hard masks (AHMs)) and silicon-based films (e.g., SiO2). x SiO x N y SiO x C y Nz This may include silicon, silicon oxide, silicon nitride, silicon oxynitride, or silicon oxycarbonitride, such as a-Si:H, polySi, or SiN, as well as their doped forms), or any other film (generally a sacrificial film) applied to facilitate patterning.

[0185] In some embodiments, the substrate is a hard mask, which is used in lithographic etching of the underlying semiconductor material. The hard mask is made of amorphous carbon (aC), SnO x SiO2, SiO x N y SiO x C, Si3N4, TiO2, TiN, W, W-doped C, WO x It may contain any of the following materials: HfO2, ZrO2, and Al2O3. For example, the substrate is preferably SnO x It may contain (such as SnO2). In various embodiments, the layer may have a thickness of 1 nm to 100 nm, or 2 nm to 10 nm.

[0186] In some non-limiting embodiments, the substrate comprises an underlayer. The underlayer may be deposited on a hard mask or other layer as described herein, and is generally located beneath the imaging layer (or film). The underlayer may be used to improve the sensitivity of the PR, increase the EUV absorptivity, and / or improve the patterning performance of the PR. If device features that create a significant topography are present on the substrate to be patterned, another important function of the underlayer may be to overlay and planarize the existing topography so that subsequent patterning steps can be performed on all areas of the focused pattern and on flat surfaces. For such applications, the underlayer (or at least one of several underlayers) may be coated using spin-coating techniques. If the PR material used has a significant inorganic component, for example, if it exhibits a metal oxide-dominant skeleton, the underlayer is advantageously a carbon-based film and may be applied by either spin-coating or a dry vacuum-based deposition process. This layer may contain various ashable hard mask (AHM) films having carbon-based and hydrogen-based compositions, and may be doped with further elements such as tungsten, boron, nitrogen, or fluorine.

[0187] In some embodiments, a surface activation operation may be used to activate a surface (e.g., the surface of a substrate and / or film) for future operation. For example, SiO x For surfaces, water or oxygen / hydrogen plasma may be used to generate hydroxyl groups on the surface. For carbon-based or hydrocarbon-based surfaces, various treatments (water, hydrogen / oxygen, CO2 plasma, or ozone treatment) may be used to generate carboxylic acid / or hydroxyl groups. Such approaches can be proven important for improving the adhesion of resist features to the substrate, as other methods may result in delamination or lifting in the solvent during handling or development.

[0188] Furthermore, adhesion may be enhanced by introducing surface roughness to increase the surface area available for interaction and to directly improve mechanical adhesion. For example, sputtering with Ar or other non-reactive ion bombardment may be used first to create a rough surface. The surface may then be terminated to have the desired surface functional groups (e.g., hydroxyl and / or carboxylic acid groups) as described above. On carbon, a combination approach may be used, where a highly reactive oxygen-containing plasma (such as CO2, O2, or H2O (or a mixture of H2 and O2)) may be used to etch away a thin layer of film with localized heterogeneity while simultaneously terminating it with -OH, -OOH, or -COOH groups. This may be performed with or without bias. In conjunction with the surface modification strategies described above, this approach can serve two purposes: surface roughening and chemical activation of the substrate surface, either for direct adhesion to inorganic metal oxide resists or as an intermediate surface modification for further functionalization.

[0189] In various embodiments, the surface (e.g., of a substrate and / or film) comprises exposed hydroxyl groups on the surface. Generally, the surface may be any surface that comprises an exposed hydroxyl surface or has been treated to produce an exposed hydroxyl surface. Such hydroxyl groups may be formed on the surface by surface treatment of the substrate using oxygen plasma, water plasma, or ozone. In other embodiments, the surface of the film may be treated to provide exposed hydroxyl groups, and a capping layer may be applied thereon. In various embodiments, the hydroxy-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.

[0190] EUV exposure treatment EUV exposure of a film can provide EUV-exposed regions having activated reaction centers containing metal atoms (M), which are generated by EUV-induced cleavage events. Such reaction centers may include metal dangling bonds, MH groups, cleaved M-ligand groups, dimerized MM bonds, or MOM crosslinks. In other embodiments, EUV exposure provides crosslinked organic moieties by photopolymerization of ligands within the film, or EUV exposure releases gaseous byproducts resulting from the photodegradation of bonds within ligands.

[0191] EUV lithography may have wavelengths in the range of approximately 10 nm to 20 nm (10 nm to 15 nm (e.g., 13.5 nm)) in a vacuum atmosphere. In particular, patterning can provide EUV-exposed and non-EUV-exposed areas for forming a pattern.

[0192] This technique includes not only EUV patterning but also DUV or electron beam patterning. In such patterning, radiation is focused on one or more regions of the imaging layer. Exposure is typically performed such that the imaging layer film includes one or more regions that are not exposed to radiation. The resulting imaging layer, containing multiple exposed and unexposed regions, can create a pattern that corresponds to the creation of transistors or other features of semiconductor devices formed by adding or removing material from the substrate in subsequent processing of the substrate. Among those useful herein, the EUV, DUV, and electron beam emission methods and apparatus include well-known methods and apparatus.

[0193] In some EUV lithography techniques, organic hard masks (e.g., ashable hard masks of PECVD amorphous carbon hydride) are patterned. During photoresist exposure, EUV radiation is absorbed by the resist and the underlying substrate, generating high-energy photoelectrons (e.g., approximately 100 eV), followed by a cascade of low-energy secondary electrons (e.g., approximately 10 eV) that diffuse laterally by a few nanometers. These electrons increase the rate of chemical reactions in the resist that enhance EUV dose sensitivity. However, the inherently random secondary electron pattern is superimposed onto the optical image. This undesirable secondary electron exposure results in reduced resolution, observable line edge roughness (LER), and linewidth variations in the patterned resist. These defects are carried over to the patterned material during subsequent pattern transfer etching.

[0194] This specification discloses a vacuum-integrated metal hard mask processing method and associated vacuum-integrated hardware that combines film formation (deposition / condensation) and optical lithography, thereby significantly improving the performance of EUV lithography (EUVL) (for example, by reducing line edge roughness).

[0195] In various embodiments described herein, a vapor deposition (e.g., condensation) process (e.g., ALD or MOCVD performed with a PECVD tool such as Lam Vector®, or a spin-on process) may be used to form a thin film of a metal-containing film, such as a photosensitive metal salt or metal-containing organic compound (organometallic compound) that has a strong absorption effect on EUV (e.g., wavelengths on the order of 10 nm to 20 nm) at the wavelength of an EUVL light source (e.g., 13.5 nm = 91.8 eV). This film is photodegraded during EUV exposure to form a metal mask, which is a pattern transfer layer, during subsequent etching (e.g., in a conductive etching tool such as Lam 2300® Kiyo®).

[0196] After deposition, the EUV-patternable thin film is typically patterned by exposure to a beam of EUV light under relatively high vacuum. The metal-containing film is then deposited in a chamber integrated with a lithography platform (e.g., a wafer stepper such as the TWINSCAN NXE:3300B® from ASML (Veldhogen, Netherlands)) and transported under vacuum to prevent reaction before exposure. Integration with the lithography tool is facilitated by the fact that EUVL also requires very low pressure, given the strong light absorption of incident photons by ambient gases (H2O, O2, etc.). In other embodiments, photosensitive metal film deposition and EUV exposure may be performed in the same chamber. In yet another embodiment, photosensitive metal film deposition and EUV exposure may be performed in different chambers.

[0197] Developing process including wet development EUV-exposed or unexposed regions can be removed by any useful development process. In one embodiment, the EUV-exposed region may have activated reaction centers, such as metal dangling bonds, MH groups, or dimerized MM bonds. In certain embodiments, MH groups can be selectively removed using one or more development processes. In other embodiments, MM bonds can be removed using a wet development process (e.g., soluble M(OH) n The base can be selectively removed (using high-temperature ethanol and water). In yet another embodiment, the EUV-exposed area is removed using wet development (e.g., using a positive-tone developer). In some embodiments, the non-EUV-exposed area is removed using wet development (e.g., using a negative-tone developer).

[0198] In some embodiments, dry and wet operations may be combined to provide a dry / wet treatment. For any of the treatments specified herein (e.g., lithography, vapor deposition, EUV exposure, development, pretreatment, post-coating treatment, etc.), various specific operations may include wet, dry, or wet / dry embodiments. For example, wet vapor deposition may be combined with wet development, or dry vapor deposition may be combined with wet development. These may also be combined with the wet or dry pre-coating and post-coating treatments described herein.

[0199] In certain embodiments, a wet development method may be used. In certain embodiments, such a wet development method is used to remove EUV-exposed areas for the purpose of providing a positive-tone photoresist or a negative-tone resist. Non-limiting examples of wet development may include the use of an alkaline developer (e.g., an aqueous alkaline developer) containing ammonium (e.g., ammonium hydroxide (NH4OH), ammonium-based ionic liquids (e.g., tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), or other quaternary alkylammonium hydroxides), organic amines such as mono-, di-, and tri-organoamines (e.g., diethylamine, diethylamine, ethylenediamine, triethylenetetramine), or alkanolamines (e.g., monoethanolamine, diethanolamine, triethanolamine, or diethylene glycolamine). In other embodiments, the alkaline developer may be a nitrogen-containing base (e.g., chemical formula R N1 NH2, R N 1st Round N2 NH, R N1 R N2 R N3 N, or R N1 R N2 R N3 R N4 N + X N1- A compound having RN1 , R N2 , R N 3, and R N4 Each of them is independent and is an organic substituent (e.g., an optionally substituted alkyl or any substituent as described herein), or two or more bondable organic substituents, X N1- , OH - F - Cl - , Br - , I - These bases may include (or other quaternary ammonium cation species well known to those skilled in the art). These bases may also include heterocyclyl nitrogen compounds, some of which are described herein.

[0200] Other developing methods may include the use of acidic developers containing halides (e.g., HCl or HBr), organic acids (e.g., formic acid, acetic acid, or citric acid), or organofluorine compounds (e.g., trifluoroacetic acid) (e.g., aqueous acidic developers or acidic developers in organic solvents), or the use of organic developers (ketones (e.g., 2-heptanone, cyclohexanone, or acetone), esters (e.g., γ-butyrolactone or ethyl 3-ethoxypropionate (EEP)), alcohols (e.g., isopropyl alcohol (IPA)), or ethers (glycol ethers (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA))), or combinations thereof).

[0201] In certain embodiments, the positive-tone developer is an aqueous alkaline developer (e.g., containing NH4OH, TMAH, TEAH, TPAH, or TBAH). In other embodiments, the negative-tone developer is an aqueous acidic developer, an acidic developer in an organic solvent, or an organic developer (e.g., HCl, HBr, formic acid, trifluoroacetic acid, 2-heptane, IPA, PGME, PGMEA, or a combination thereof).

[0202] Post-treatment after application The methods described herein may include any useful post-treatments, as described below.

[0203] In back and bevel cleaning processes, vapor and / or plasma can be restricted to specific areas of the wafer to ensure that only the back and bevel are removed without causing any degradation of the film on the front of the wafer. The deposited EUV photoresist film to be removed is generally composed of Sn, O, and C, but the same cleaning approach can be extended to films of other metal oxide resists and materials. Furthermore, this approach can also be used for film delamination and PR correction.

[0204] Suitable processing conditions for dry bevel edge and back surface cleaning may include, depending on the photoresist film, its composition, and properties, a reaction flow rate of 100 sccm to 500 sccm (e.g., 500 sccm of HCl, HBr, or H2 and Cl2 or Br2, BCl3, or H2), a temperature of -10°C to 120°C (e.g., 20°C), a pressure of 20 mTorr to 500 mTorr (e.g., 300 mTorr), and a plasma power of 0-500 W at a high frequency (e.g., 13.56 MHz), for a period of approximately 10 to 20 seconds. While these conditions are suitable for some processing reactors (e.g., the Kiyo etching tool from Lam Research, Fremont, California), it should be understood that a wider range of processing conditions may be used depending on the performance of the processing reactor.

[0205] Photolithography typically involves one or more bake steps to facilitate the chemical reactions necessary to create a chemical difference between the exposed and unexposed areas of a photoresist. In high-volume production (HVM), such bake steps are typically performed on a track where the wafer is baked on a hot plate at a pre-set temperature under ambient air or possibly a stream of N2. More careful control of the bake atmosphere, along with introducing additional reactive gas components into the atmosphere during these bake steps, can help further reduce the required dose and / or improve pattern fidelity.

[0206] According to various aspects of this disclosure, one or more post-treatments on metal and / or metal oxide-based photoresists 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)) can increase the difference in material properties between exposed and unexposed photoresists, and thus reduce dose-to-size (DtS), improve the PR profile, and improve subsequent post-development line edge roughness and line width roughness (LER / LWR).

[0207] In post-coating treatment (e.g., PAB), the composition of the unexposed metal and / or metal oxide photoresist can be altered after deposition and before exposure by using heat treatment along with control of temperature, gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, N2O, NO, Ar, He, or mixtures thereof), or vacuum, as well as humidity. This alteration can increase the EUV sensitivity of the material, allowing for lower dose-to-size and edge roughness to be achieved after exposure and development.

[0208] In post-exposure treatment (e.g., PEB), the composition of both unexposed and exposed photoresists can be altered using heat treatment along with control of temperature, gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, N2O, NO, Ar, He, or mixtures thereof), or vacuum, as well as humidity. This alteration can increase the difference in composition / material properties between the unexposed and exposed photoresists, and the difference in development speed between them. This can thereby achieve a higher development selectivity ratio. The improved selectivity ratio can result in a more square PR profile, along with improved surface roughness and / or less photoresist residue / scum. In certain embodiments, PEB can be performed in air, in the optional presence of water vapor and CO2.

[0209] In post-development processing (e.g., post-development bake, i.e., PDB), the composition of the unexposed photoresist can be altered by heat treatment along with temperature, gas atmosphere (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), as well as humidity control. In certain embodiments, the conditions further include the use of plasma (e.g., O2, O3, Ar, He, or mixtures thereof). This alteration can increase the hardness of the material, which can be useful when the film is used as a resist mask when etching the underlying substrate.

[0210] In these cases, in other embodiments, heat treatment may be replaced with remote plasma treatment to increase the number of reactive species, thereby lowering the energy barrier for the reaction and increasing productivity. Remote plasma generates more reactive radicals, which can reduce the reaction temperature / time of the treatment, leading to increased productivity.

[0211] Therefore, one or more treatments may be applied to modify the photoresist itself to increase the development selectivity. For example, thermal or radical modification can increase the difference between unexposed and exposed materials, and thus increase the selectivity of the subsequent development process.

[0212] While we do not wish to be limited by the mechanism, wet development can be dependent on the solubility of the material. For example, heating above 220°C may significantly increase the degree of crosslinking in both the exposed and unexposed regions of a metal-containing PR film, to the point where both the exposed and unexposed regions become insoluble in the wet developing solvent. As a result, the film can no longer be reliably wet-developed. For example, baking of a metal-containing PR film that has been wet-spin-on or wet-developed may be performed at temperatures below 180°C, 200°C, or 250°C. The processing temperature in PAB, PEB, or PDB may be varied across a window to adjust and optimize the processing process, for example, from approximately 90°C to 250°C (e.g., 90°C to 190°C), 90°C to 600°C, 100°C to 400°C, 125°C to 300°C, and from approximately 170°C to 250°C or higher (e.g., 190°C to 240°C) (for example, for PAB, PEB, and / or PDB). It has been observed that as the processing temperature increases within the above ranges, a decrease in etching rate and an increase in etching selectivity occur.

[0213] In certain embodiments, the PAB, PEB, and / or PDB treatment may be performed with a gas atmosphere flow rate in the range of 100 sccm to 10,000 sccm, humidity of a few percent to a maximum of 100% (e.g., 20% to 50%), pressure between atmospheric pressure and vacuum, and a duration of about 1 to 15 minutes (e.g., about 2 minutes).

[0214] These findings can be used to adjust processing conditions for the purpose of tailoring or optimizing the process for specific materials and environments. For example, when PEB heat treatment is performed at 220°C to 250°C for about 2 minutes in air with about 20% humidity, the selectivity ratio achieved for a given EUV dose may be equivalent to the selectivity ratio for an EUV dose about 30% higher than that achieved without such heat treatment. Therefore, depending on the selectivity requirements / constraints of the semiconductor processing operation, the required EUV dose can be reduced using heat treatments such as those described herein. Alternatively, if a higher selectivity ratio is required and a higher dose is acceptable, a much higher selectivity ratio (up to 100 times the exposed-to-unexposed selectivity ratio) can be obtained than is possible in the context of wet development.

[0215] Further steps may include in-situ measurements that allow for the evaluation of physical and structural features (e.g., critical dimensions, film thickness, etc.) during the photolithography process. Modules for implementing in-situ measurements include, for example, a scattermeter, deflection analysis, downstream mass spectrometry, and / or a plasma-enhanced downstream emission spectroscopy module.

[0216] Device The disclosure also includes any apparatus configured to perform any of the methods described herein. In one embodiment, an apparatus for depositing a film comprises a deposition module having a chamber for depositing an EUV-sensitive material as a film by providing a metal precursor in the selective presence of a reactant; a patterning module having an EUV photolithography tool having a radiation source with a wavelength of less than 30 nm; and a developing module having a chamber for developing the film in the presence of a metal chelating agent.

[0217] The apparatus may further include a controller having instructions for such modules. In one embodiment, the controller comprises one or more memory devices, one or more processors, and system control software coded with instructions for performing film deposition. instructionIn the deposition module, a metal precursor is deposited as a film on the upper surface of a substrate or photoresist layer; in the patterning module, a pattern is formed within the film by directly patterning the film with a resolution of less than 30 nm using EUV exposure; and in the developing module, the film is developed in the presence of a metal chelating agent. Command for This may include: In certain embodiments, the developing module provides removal of EUV-exposed or non-EUV-exposed areas, thereby providing a pattern within the film.

[0218] Figure 4 shows one embodiment of a multi-station processing tool 400 (such as the VECTOR® processing tool from Lam Research, Inc., Fremont, California). The processing stations may be configured as modules within a cluster tool. Figure 6 shows a semiconductor processing cluster tool architecture comprising a vacuum-integrated deposition module and a patterning module suitable for implementing the embodiments described herein. Such a cluster processing tool architecture may include modules for resist deposition, resist exposure (EUV scanner), resist development, and etching, as described herein with reference to Figures 5 and 6.

[0219] In some embodiments, some of the processing functions may be performed sequentially within the same module. Embodiments of the present disclosure are directed to a method and apparatus for receiving a wafer containing a photopatterned EUV resist thin film layer placed on a layer stack to be etched after photopatterning in an EUV scanner, as described herein, into a developing / etching chamber (e.g., a wet developing / etching chamber), developing the photopatterned EUV resist thin film layer, and then etching the underlying layer using the patterned EUV resist as a mask.

[0220] A wet developing chamber may be any chamber configured to supply a developer to an exposed film or substrate. In one example, the chamber may contain a wet developer, and the exposed film or substrate is immersed in the wet developer (e.g., in immersion developing). In another example, the chamber may be equipped with one or more showerheads, sprays, nozzles, dispensers, etc., to supply the wet developer to the exposed film or substrate (e.g., in spray-on developing).

[0221] The substrate is then provided into the chamber and may be placed on a pedestal. For example, the substrate may be placed below the dispenser and resting on the pedestal. In some embodiments, the pedestal may be raised and lowered to expose the substrate to the space between the substrate and the showerhead. Furthermore, the pedestal may be rotated during the supply of the wet developer. Thus, in some embodiments, the pedestal may have a pivot axis for rotating the substrate. In some embodiments, it can be seen that one or more of these adjustments may be performed programmatically by one or more suitable computer controllers.

[0222] As described above, one or more processing stations may be included in the multi-station processing tool. Figure 4 is a schematic diagram showing one embodiment of a multi-station processing tool 400, which includes an inlet load lock 402 and an outlet load lock 404, one or both of which may include a remote plasma source. A robot 406 under atmospheric pressure is configured to move a wafer from a cassette loaded through a pod 408 into the inlet load lock 402 via an atmospheric port 410. Once the wafer is placed on a pedestal 412 in the inlet load lock 402 by the robot 406, the atmospheric port 410 is closed, and the load lock is pumped evacuated. If the inlet load lock 402 includes a remote plasma source, the wafer may undergo remote plasma treatment to treat the silicon nitride surface within the load lock before being introduced into the processing chamber 414. Furthermore, the wafer may be heated within the inlet load lock 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) loads the wafer into the reactor for processing and places it on the pedestal of the first station shown inside the reactor. The embodiment shown in Figure 4 includes a load lock, but it can be seen that in some embodiments the wafer may be loaded directly into the processing station.

[0223] The processing chamber 414 in the figure comprises four processing stations numbered 1 to 4 in the embodiment shown in Figure 4. Each station has a heated pedestal (shown as 418 for station 1) and a gas line inlet. In some embodiments, each processing station may serve a different or multiple purpose. Although the processing chamber 414 in the figure comprises four stations, a processing chamber according to this disclosure may have any suitable number of stations. For example, in some embodiments, the processing chamber may have five or more stations, and in other embodiments, the processing chamber may have three or fewer stations.

[0224] Figure 4 shows one embodiment of a wafer handling system 490 for moving wafers within a processing chamber 414. In some embodiments, the wafer handling system 490 can move wafers between various processing stations and / or between processing stations and load locks. It can be seen that any suitable wafer handling system may be used. Non-limiting examples include wafer carousels and wafer handler robots. Figure 4 further shows one embodiment of a system controller 450 used to control processing conditions and hardware states of a processing tool 400. The system controller 450 may comprise one or more memory devices 456, one or more mass storage devices 454, and one or more processors 452. The processors 452 may comprise a CPU or computer, analog and / or digital input / output connections, a stepper motor controller board, and the like.

[0225] In some embodiments, the system controller 450 controls all operations of the processing tool 400. The system controller 450 is stored in a mass storage device 454, loaded into a memory device 456, and runs system control software 458 executed by a processor 452. Alternatively, the control logic may be hardcoded into the controller 450. For these purposes, application-specific integrated circuits, programmable logic devices (e.g., field-programmable gate arrays, i.e., FPGAs) may be used. Wherever “software” or “code” is used below, functionally equivalent hardcoded logic may be used instead. The system control software 458 may include instructions 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 pedestal, chuck, and / or susceptor position, and other parameters of specific processing performed by the processing tool 400. The system control software 458 may be configured in any suitable manner. For example, various processing tool component subroutines or control objects may be written to control the operation of processing tool components used to perform processing for various processing tools. The system control software 458 may be coded in any suitable computer-readable programming language.

[0226] In some embodiments, the system control software 458 may include input / output control (IOC) sequence instructions for controlling the various parameters described above. In some embodiments, other computer software and / or programs stored in the mass storage device 454 and / or memory device 456 associated with the system controller 450 may be used. Examples of programs or program sections for this purpose include a substrate positioning program, a processing gas control program, a pressure control program, a heater control program, and a plasma control program.

[0227] The substrate positioning program may include program code for processing tool components used to load the substrate onto the pedestal 418 and to control the spacing between the substrate and other components of the processing tool 400.

[0228] The processing gas control program may include code for controlling the composition and flow rate of various gases (e.g., HBr or HCl gas, as described herein), and optionally for flowing gas into one or more processing stations before deposition to stabilize the pressure within the processing stations. The pressure control program may include code for controlling the pressure within the processing stations by adjusting, for example, the throttle valve of the processing station's exhaust system, the gas flow rate to the processing station, etc.

[0229] The heater control program may include code for controlling the current to the heating unit used to heat the substrate. Alternatively, the heater control program may control the supply of a heat-conducting gas (such as helium) to the substrate.

[0230] The plasma control program may include code for setting RF power levels applied to processing electrodes in one or more processing stations, according to embodiments of this specification.

[0231] The pressure control program may include code for maintaining the pressure in the reaction chamber, according to the embodiments herein.

[0232] In some embodiments, a user interface associated with the system controller 450 may exist. The user interface may include a display screen (a graphical software display of the device and / or processing conditions) and user input devices such as a pointing device, keyboard, touchscreen, and microphone.

[0233] In some embodiments, the parameters adjusted by the system controller 450 may relate to processing conditions. Non-limiting examples include the composition and flow rate of the processing gas, temperature, pressure, and plasma conditions (such as RF bias power level). These parameters may be provided to the user in the form of a recipe and can be input using a user interface.

[0234] Signals for monitoring the process may be provided from various processing tool sensors via analog and / or digital input connections to the system controller 450. Signals for controlling the process may be output from analog and digital output connections to the processing tool 400. Non-limiting examples of processing tool sensors that can be monitored include mass flow controllers, pressure sensors (such as pressure gauges), and thermocouples. Appropriately programmed feedback and control algorithms may be used in conjunction with data from these sensors to maintain processing conditions.

[0235] The system controller 450 may provide program instructions for carrying out the deposition process described above. These program instructions may control various process parameters, such as DC power level, RF bias power level, pressure, and temperature. The instructions may also control parameters to operate the development and / or etching process according to the various embodiments described herein.

[0236] The system controller 450 typically comprises one or more memory devices and one or more processors configured to execute instructions so that the device performs a method according to the disclosed embodiments. A machine-readable medium containing instructions for controlling processing operations according to the disclosed embodiments may be connected to the system controller 450.

[0237] In some embodiments, the system controller 450 is part of a system, and the system may be part of the examples described above. Such a system may comprise a semiconductor processing apparatus, including one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (such as a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronic equipment for controlling the operation of the system before, during, and after processing of semiconductor wafers or substrates. The electronic equipment may be referred to as a “controller” and may control various components or sub-components of the system. Depending on the processing conditions and / or the type of system, the system controller 450 may be programmed to control any of the processing disclosed herein, such as the supply 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 supply settings, position and operation settings, and wafer movement in and out of a load lock connected to or coupled with tools and other moving tools and / or specific systems.

[0238] Generally, the system controller 450 may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. Integrated circuits may include chips in the form of firmware that store program instructions, chips defined as digital signal processors (DSPs), application-specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions that are communicated to the system controller 450 in the form of various individual settings (or program files) and define operating parameters for performing specific operations on or for semiconductor wafers, or operating parameters to the system. In some embodiments, operating parameters may be part of a recipe defined by a process engineer to achieve one or more processing steps during the processing of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0239] In some embodiments, the system controller 450 may be part of a computer integrated with the system, connected to the system, networked with the system in other ways, or a combination thereof, or connected to such a computer. For example, the system controller 450 may be in the “cloud” or may be all or part of a fab host computer system that enables remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, examine the history of past manufacturing operations, or examine trends or performance metrics from multiple manufacturing operations, in order to change the parameters of the current operation, set up a processing step according to the current operation, or start a new operation. In some examples, a remote computer (e.g., a server) may provide processing recipes to the system via a network (which may include a local network or the internet). The remote computer may have a user interface that enables input or programming of parameters and / or settings, which are communicated from the remote computer to the system. In some examples, the system controller 450 receives instructions in the form of data, which specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of processing to be performed and the type of tools that the system controller 450 is configured to interface with or control. Thus, as described above, the system controller 450 may be distributed, for example, by comprising one or more separate controllers that are networked and operate toward a common purpose (such as the processing and control described herein). An example of a distributed controller for such a purpose is one or more integrated circuits on the chamber that communicate with one or more remotely located integrated circuits (located at the platform level, or as part of a remote computer, etc.) that cooperate to control the processing in the chamber.

[0240] Examples of systems, though not limited to them, may include plasma etching chambers or modules, deposition chambers or modules, spin rinse 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, 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, wet development chambers or modules, and any other semiconductor processing systems related to or that may be used in the processing and / or manufacturing of semiconductor wafers.

[0241] As described above, depending on one or more processing steps performed by the tool, the system controller 450 may communicate with one or more of the following: other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, the main computer, another controller, or tools used for material transport to and from the tool locations and / or load ports within the semiconductor manufacturing plant.

[0242] In certain embodiments, inductively coupled plasma (ICP) reactors that may be suitable for etching operations suitable for implementing some embodiments are described here. While ICP reactors are described herein, it should be understood that capacitively coupled plasma reactors may be used in some embodiments.

[0243] Figure 5 is a cross-sectional view showing an inductively coupled plasma apparatus 500 suitable for carrying out a particular embodiment or aspect of an embodiment, such as etching, an example of which is the Kiyo® reactor manufactured by Lam Research, Inc. of Fremont, California. In other embodiments, other tools or tool types having the capability to perform the etching process described herein may be used for implementation.

[0244] The inductively coupled plasma apparatus 500 comprises an overall processing chamber structurally defined by a chamber wall 501 and a window 511. The chamber wall 501 may be made of stainless steel or aluminum. The window 511 may be made of quartz or other dielectric material. An optional internal plasma grid 550 divides the overall processing chamber into an upper sub-chamber 502 and a lower sub-chamber 503. In most embodiments, the chamber space formed by the sub-chambers 502 and 503 can be utilized by removing the plasma grid 550. A chuck 517 is located near the bottom inner surface within the lower sub-chamber 503. The chuck 517 is configured to receive and hold a semiconductor wafer 519 on which etching and deposition processes are performed. The chuck 517 may be an electrostatic chuck for supporting the wafer 519 when the wafer is present. In some embodiments, an edge ring (not shown) surrounds the chuck 517 and has an upper surface that is substantially coplanar with the upper surface of the wafer 519 when the wafer is on the chuck 517. The chuck 517 also includes electrostatic electrodes for chucking and dechucking the wafer 519. A filter and a DC clamp power supply (not shown) may be provided for this purpose.

[0245] Other control systems for lifting the wafer 519 from the chuck 517 may also be provided. The chuck 517 may be charged using an RF power supply 523. The RF power supply 523 is connected to a matching circuit 521 through a connection 527. The matching circuit 521 is connected to the chuck 517 through a connection 525. Thus, the RF power supply 523 is connected to the chuck 517. In various embodiments, the bias power of the electrostatic chuck may be set to about 50V or to a different bias power, depending on the processing performed according to the disclosed embodiments. For example, the bias power may be about 20V to about 100V, or about 30V to about 150V.

[0246] Elements for plasma generation include a coil 533 positioned above the window 511. In some embodiments, the coil is not utilized in the disclosed embodiments. The coil 533 is manufactured from a conductive material and includes at least one complete winding. An example of a coil 533 shown in Figure 5 includes three windings. Cross-sections of the coil 533 are indicated by symbols, where the "X" coil rotates and extends from the front to the back of the paper, and the "●" coil rotates and extends from the back to the front of the paper. Elements for plasma generation also include 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 through connection 545. The matching circuit 539 is connected to the coil 533 through connection 543. Thus, the RF power supply 541 is connected to the coil 533. An optional Faraday shield 549 is positioned between the coil 533 and the window 511. The Faraday shield 549 may be maintained in a spaced-out relationship with respect to the coil 533. In some embodiments, the Faraday shield 549 is positioned directly above the window 511. In some embodiments, the Faraday shield is located between the window 511 and the chuck 517. In some embodiments, the Faraday shield is not maintained in a spaced-out relationship with respect to the coil 533. For example, the Faraday shield may be directly below the window without a gap. The coil 533, the Faraday shield 549, and the window 511 are each configured to be substantially horizontal to each other. The Faraday shield 549 can prevent metal or other species from being deposited on the window 511 of the processing chamber.

[0247] The process gas may be introduced into the processing chamber through one or more main gas inlets 560 located within the upper sub-chamber 502, and / or through one or more side gas inlets 570. Similarly, although not explicitly shown, similar gas inlets may be used to supply the process gas to the capacitively coupled plasma processing chamber. A vacuum pump (e.g., a one or two-stage mechanical dry pump and / or turbomolecular pump) 540 may be used to draw the process gas from the processing chamber and to maintain the pressure within the processing chamber. For example, the vacuum pump may be used to evacuate the lower sub-chamber 503 during the purging operation of the ALD. Valve-controlled conduits may be used to fluidly connect the vacuum pump to the processing chamber to selectively control the application of the vacuum environment provided by the vacuum pump. This may be done using closed-loop controlled flow limiting devices such as throttle valves (not shown) or pendulum valves (not shown) during working plasma processing. Similarly, a vacuum pump and a valve-controlled fluid connection to the capacitively coupled plasma processing chamber may be used.

[0248] During the operation of the apparatus 500, one or more process gases may be supplied through the gas inlets 560 and / or 570. In certain embodiments, the process gas may be supplied only through the main gas inlet 560 or only through the side gas inlets 570. In some cases, the gas inlets shown in the figure may be replaced, for example, with more complex gas inlets, one or more showerheads. The Faraday shield 549 and / or optional grid 550 may have internal channels and holes that allow for the supply of process gas to the process chamber. One or both of the Faraday shield 549 and / or optional grid 550 may function as showerheads for the supply of process gas. In some embodiments, a liquid vaporization / supply system may be located upstream of the process chamber so that a liquid reactant or precursor is vaporized and the vaporized reactant or precursor is introduced into the process chamber via the gas inlets 560 and / or 570.

[0249] High-frequency power is supplied from the RF power supply 541 to the coil 533, causing an RF current to flow through the coil 533. The RF current flowing through the coil 533 generates an electromagnetic field around the coil 533. The electromagnetic field generates an induced current in the upper sub-chamber 502. The physical and chemical interactions between the various ions and radicals generated and the wafer 519 etch the features of the wafer 519 and selectively deposit layers onto the wafer 519.

[0250] When the plasma grid 550 is utilized so that both an upper sub-chamber 502 and a lower sub-chamber 503 are present, the induced current acts on the gas present in the upper sub-chamber 502 to generate an electron-ion plasma within the upper sub-chamber 502. An optional internal plasma grid 550 limits the amount of hot electrons in the lower sub-chamber 503. In some embodiments, the apparatus 500 is designed and operated so that the plasma present in the lower sub-chamber 503 is an ion-ion plasma.

[0251] Both the upper electron-ion plasma and the lower ion-ion plasma contain positive and negative ions, but the ion-ion plasma has a larger ratio of negative ions to positive ions. Volatile etching byproducts and / or deposition byproducts may be removed from the lower sub-chamber 503 through port 522. The chuck 517 disclosed herein may be operated at high temperatures in the range of about 10°C to about 250°C. The temperature depends on the processing operation and the individual recipe.

[0252] The apparatus 500 may be connected to equipment (not shown) when installed in a cleanroom or manufacturing facility. This equipment includes piping that provides processing gas, vacuum, temperature control, and environmental particle control. These components are connected to the apparatus 500 when installed in the target manufacturing facility. Furthermore, the apparatus 500 may be connected to a transfer chamber that allows for the transfer of semiconductor wafers into and out of the apparatus 500 using robotic technology with typical automation.

[0253] In some embodiments, a system controller 530 (which may include one or more physical or logical controllers) controls some or all of the operation of the processing chamber. The system controller 530 may comprise one or more memory devices and one or more processors. In some embodiments, the apparatus 500 comprises a switching system for controlling flow rate and duration when the disclosed embodiment is performed. In some embodiments, the apparatus 500 may have a switching time of up to about 600 ms or up to about 750 ms. The switching time may depend on flow chemistry, selected recipe, reactor architecture, and other factors.

[0254] In some embodiments, the system controller 530 is part of a system, and the system may be part of the examples described above. Such a system may comprise a semiconductor processing apparatus, including one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (such as a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronic equipment for controlling the operation of the system before, during, and after processing of semiconductor wafers or substrates. The electronic equipment may be integrated with the system controller 530, which can control various components or sub-components of the system. Depending on the processing parameters and / or the type of system, the system controller may be programmed to control any of the processing disclosed herein, such as the supply 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 supply settings, position and operation settings, and wafer movement in and out of a load lock connected to or coupled with tools and other moving tools and / or specific systems.

[0255] Generally, the system controller 530 may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, and so on. Integrated circuits may include chips in the form of firmware that store program instructions, chips defined as digital signal processors (DSPs), application-specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions that are communicated to the controller in the form of various individual settings (or program files) and define operating parameters for performing specific operations on or for semiconductor wafers, or operating parameters to the system. In some embodiments, operating parameters may be part of a recipe defined by a processing engineer to achieve one or more processing steps during processing or removal of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0256] In some embodiments, the system controller 530 may be part of a computer integrated with the system, connected to the system, networked with the system in other ways, or a combination thereof, or connected to such a computer. For example, the controller may be in the “cloud” or may be all or part of a fab host computer system that enables remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, examine the history of past manufacturing operations, or examine trends or performance metrics from multiple manufacturing operations, in order to change the parameters of the current operation, set up a processing step according to the current operation, or start a new operation. In some examples, a remote computer (e.g., a server) may provide processing recipes to the system via a network (which may include a local network or the internet). The remote computer may have a user interface that enables input or programming of parameters and / or settings, which are communicated from the remote computer to the system. In some examples, the system controller 530 receives instructions in the form of data, which specify parameters for each of the processing steps performed during one or more operations. It should be understood that the parameters may be specific to the type of processing to be performed and the type of tool the controller is configured to interface with or control. Therefore, as described above, the system controller 530 may be distributed, for example, by comprising one or more separate controllers that are networked and operate toward a common purpose (such as the processing and control described herein). An example of a distributed controller for such a purpose is one or more integrated circuits on the chamber that communicate with one or more remotely located integrated circuits (located at the platform level, or as part of a remote computer, etc.) that cooperate to control the processing in the chamber.

[0257] Examples of systems, though not limited to them, may include plasma etching chambers or modules, deposition chambers or modules, spin rinse 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, ALD chambers or modules, ALE chambers or modules, ion implantation chambers or modules, track chambers or modules, EUV lithography chambers (scanners) or modules, wet developing chambers or modules, and any other semiconductor processing systems related to or that may be used in the processing and / or manufacturing of semiconductor wafers.

[0258] As described above, depending on the one or more processing steps performed by the tool, the controller may communicate with one or more of the following: other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, the main computer, another controller, or tools used for material transport to and from the tool locations and / or load ports within the semiconductor manufacturing plant.

[0259] EUVL patterning may be performed using any suitable tool (often called a scanner), such as the TWINSCAN NXE:3300B® platform from ASML in Veldhoven, Netherlands. The EUVL patterning tool may be a standalone apparatus into which the substrate is loaded and unloaded for deposition and etching as described herein. Alternatively, as described below, the EUVL patterning tool may be a module on a large multi-component tool. Figure 6 shows a semiconductor processing cluster tool architecture suitable for performing the process described herein, comprising a vacuum-integrated deposition module, an EUV patterning module, and a develop / etching module connected to a vacuum transfer module. The process may be performed without using such a vacuum-integrated apparatus, although such an apparatus may be advantageous in some embodiments.

[0260] Figure 6 shows a semiconductor processing cluster tool architecture with vacuum-integrated deposition and patterning modules connected to a vacuum transfer module, suitable for performing the processes described herein. The arrangement of transfer modules that "transfer" wafers between multiple storage facilities and processing modules is sometimes referred to as a "cluster tool architecture" system. The deposition and patterning modules are vacuum-integrated according to the requirements of the specific process. Other modules, such as those for etching, may be provided in the cluster.

[0261] A vacuum transfer module (VTM) 638 is connected to four processing modules 620a–620d, which may be individually optimized to perform various processing operations. For example, processing modules 620a–620d may be implemented to perform deposition, evaporation, ELD, development, etching, stripping, and / or other semiconductor processing. For example, module 620a may be an ALD reactor capable of performing thermal atomic layer deposition in a non-plasma environment as described herein, such as the Vector tool from Lam Research, Fremont, California. Module 620b may be a PECVD tool such as Lam Vector®. Please note that the drawings are not necessarily drawn to scale.

[0262] Airlocks 642 and 646 (also known as load locks or transfer modules) are connected to the VTM638 and patterning module 640. For example, as mentioned above, a suitable patterning module could be the TWINSCAN NXE:3300B® platform from ASML in Veldhogen, Netherlands. This tool architecture allows the workpiece (such as a semiconductor substrate or wafer) to be transported under vacuum so as not to react before exposure. The integration of the deposition module and lithography tool is facilitated by the fact that EUVL also requires very low pressure, given the strong light absorption of incident photons by the surrounding gas (H2O, O2, etc.).

[0263] As described above, this integrated architecture is merely one possible embodiment of the tools for performing the described process. The process may also be performed by a standalone EUVL scanner and an deposition reactor (such as the Lam Vector tool) integrated as a module in a cluster architecture, together with other tools (e.g., Lam Kiyo or Gamma tools) such as etching and stripping, except that there is no standalone or, for example, integrated patterning module, as described with reference to Figure 6.

[0264] Airlock 642 may be an "export" load lock, referring to the removal of a substrate from the VTM 638 supplying the deposition module 620a to the patterning module 640, and airlock 646 may be an "input" load lock, referring to the return of a substrate from the patterning module 640 to the VTM 638. The input load lock 646 may also provide an interface with the tool outside for substrate access and ejection. Each processing module has a facet connecting the module to the VTM 638. For example, the deposition processing module 620a has a facet 636. Within each facet, sensors (e.g., sensors 1-18 in the figure) are used to detect the passage of the wafer 626 as it moves between the respective stations. The patterning module 640 and the airlocks 642 and 646 may also have further facets and sensors, which are not shown.

[0265] A main VTM robot 622 transfers the wafer 626 between modules, including airlocks 642 and 646. In one embodiment, the robot 622 has one arm, and in another embodiment, the robot 622 has two arms, each arm having an end effector 624 for grasping the wafer (such as wafer 626) for transfer. A front-end robot 644 is used to transfer the wafer 626 from the unloading airlock 642 to the patterning module 640 and from the patterning module 640 to the loading airlock 646. The front-end robot 644 may also transport the wafer 626 between the loading load lock and the outside of the tool for substrate access and unloading. The loading airlock module 646 can be adapted to an environment between air and vacuum so that the wafer 626 can move between the two pressure environments without damage.

[0266] It should be noted that EUVL tools typically operate under higher vacuum than deposition tools. In this case, it is preferable to increase the vacuum environment of the substrate during transport from the deposition tool to the EUVL tool to allow degassing of the substrate before it enters the patterning tool. The unloading airlock 642 provides this function by holding the wafer to be transported at a lower pressure (below the pressure inside the patterning module 640) for a certain period of time and venting all off-gases so that the optics of the patterning tool 640 are not contaminated by off-gases from the substrate. A suitable pressure for the unloading off-gas airlock is 1E-8 Torr or less.

[0267] In some embodiments, a system controller 650 (which may include one or more physical or logical controllers) controls some or all of the operation of the cluster tools and / or separate modules thereof. Note that the controller may be located locally in the cluster structure, or it may be located outside the cluster structure, i.e., at a separate location, within the manufacturing floor and connected to the cluster structure via a network. The system controller 650 may comprise one or more memory devices and one or more processors. The processor may comprise a central processing unit (CPU) or computer, analog and / or digital input / output connections, a stepper motor controller board, and other similar components. Instructions for performing appropriate control operations are executed by the processor. These instructions may be stored in memory devices associated with the controller or provided via a network. In certain embodiments, the system controller runs system control software.

[0268] The system control software may include instructions for controlling the timing and / or extent of the application of any aspect of tool or module operation. The system control software may be configured in any suitable manner. For example, various processing tool component subroutines or control objects may be written to control the operation of processing tool components necessary to perform the processing of various processing tools. The system control software may be coded in any suitable computer-readable programming language. In some embodiments, the system control software includes input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each stage of a semiconductor manufacturing process may include one or more instructions for execution by the system controller. Instructions for setting processing conditions for condensation, deposition, evaporation, patterning, and / or etching stages may be included, for example, in the corresponding recipe stage.

[0269] In various embodiments, apparatuses for forming negative pattern masks are provided. The apparatus may comprise a processing chamber for patterning, deposition, and etching, and a controller including instructions for forming a negative pattern mask. The instructions may include code for patterning features in a chemically amplified (CAR) resist on a semiconductor substrate by EUV exposure to expose the substrate surface within the processing chamber, developing the photopatterned resist, and etching the underlying layer or lower stack using the patterned resist as a mask.

[0270] It should be noted that the computer controlling wafer movement may be located locally within the cluster architecture, or it may be located outside the cluster architecture on the manufacturing floor, i.e., at a separate location, and connected to the cluster architecture via a network.

[0271] knot For the sake of understanding, this embodiment has been described in some detail, but it is clear that some modifications and alterations may be made within the scope of the appended claims. The embodiments disclosed herein can be implemented without some or all of these specific details. Furthermore, detailed descriptions of well-known processing operations have been omitted to avoid unnecessarily obscuring the disclosed embodiments. In addition, while the disclosed embodiments are described in relation to specific embodiments, it should be understood that the specific embodiments are not intended to limit the disclosed embodiments. Note that there are many other ways of carrying out the processing, system, and apparatus of the present invention. Therefore, this embodiment is considered illustrative and not limiting, and embodiments are not limited to the details shown herein. This disclosure may be implemented in the following forms. [Form 1] It is a method, A step of providing a radiation-patterned film having an interface region positioned between a radiation-exposed region and a non-radiation-exposed region, or positioned within a radiation-exposed region, wherein the interface region comprises a radiation-exposed metal center. A step of developing the radiation-patterned film in the presence of a metal chelating agent, wherein the metal chelating agent is configured to bond to the radiation-exposed metal centers in the interface region, A method that includes [a certain feature]. [Form 2] A method according to Embodiment 1, wherein the radiation-patterned film includes an extreme ultraviolet (EUV) sensitive film. [Form 3] A method according to Embodiment 2, wherein the interface region includes a transition region located between at least one EUV exposure region and at least one EUV non-exposure region. [Form 4] A method according to Embodiment 2, wherein the developing step further includes a step of removing the interface region. [Form 5] A method according to Embodiment 2, wherein the developing step further includes a step of using a solvent or solvent mixture that preferentially removes the radiation-exposed region compared to the radiation-unexposed region. [Form 6] A method according to Embodiment 5, wherein the metal chelating agent is soluble in the solvent or a mixture of the solvents. [Form 7] A method according to Embodiment 2, wherein the metal chelating agent preferentially bonds to the radiation-exposed metal centers in the interface region compared to the metal centers present in the non-radiation-exposed region. [Form 8] A method according to Forms 2 to 7, wherein the metal chelating agent comprises a dicarbonyl, diol, carboxylic acid, diacid, triacid, hydroxycarboxylic acid, hydroxamic acid, hydroxylactone, hydroxyketone, or a salt thereof. [Form 9] A method according to Embodiment 8, wherein the metal chelating agent comprises formic acid, citric acid, acetylacetone, salicylic acid, catechol, or ascorbic acid. [Form 10] A method according to the method of form 8, wherein the dicarbonyl is a 1,3-diketone. [Form 11] A method according to Embodiment 8, wherein the carboxylic acid comprises RA1-CO2H, and RA1 is H, optionally substituted alkyl, optionally substituted hydroxyalkyl, optionally substituted hydroxyaryl, optionally substituted carboxyalkyl, optionally substituted carboxyaryl, or optionally substituted aryl. [Form 12] A method according to Embodiment 8, wherein the hydroxamic acid comprises RA1-C(O)NRA2OH, and each of RA1 and RA2 is independently H, an optionally substituted alkyl, or an optionally substituted aryl. [Form 13] A method according to Embodiment 8, wherein the hydroxyketone comprises hydroxypyridinone, hydroxypyrimidone, or hydroxypyrone. [Form 14] The method according to Embodiment 8, wherein the hydroxyketone has the structure of the following chemical formula (I), (II), or (III): [C1], [C2], [C3], Or, containing those salts, Each of X1 and X2 is independent and has -CR1= or -N=, Each R1 and R2 is independently H, optionally substituted alkyl, optionally substituted hydroxyalkyl, optionally substituted carboxyalkyl, -C(O)NRN1RN2, or -C(O)ORO1, where each of RN1, RN2, and RO1 is independently H, optionally substituted alkyl, or optionally substituted alkyl, and optionally RN1 and RN2 collectively form optionally substituted heterocyclines. A method in which R3 is independently H, an optionally substituted alkyl, or an optionally substituted aryl. [Form 15] A method according to Forms 2 to 7, wherein the metal chelating agent comprises a plurality of parts arranged on a skeleton, the plurality of parts being selected from the group consisting of hydroxyl, carboxyl, amide, amino, and oxo. [Form 16] A method according to Embodiment 15, wherein the plurality of parts comprise a monovalent or polyvalent dicarbonyl, diol, carboxylic acid, diacid, triacid, hydroxycarboxylic acid, hydroxamic acid, hydroxylactone, hydroxyketone, or a salt thereof. [Form 17] A method according to Embodiment 2, wherein the radiation-exposed metal center comprises a transition metal. [Form 18] A method according to Embodiment 2, wherein the radiation-exposed metal center comprises tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), or tantalum (Ta). [Form 19] A method according to Embodiment 2, wherein the radiation-patterned film comprises a metal oxide film or an organometallic oxide film. [Form 20] The method according to Embodiment 19, wherein the radiation-patterned film is formed from a metal precursor having a structure of the following chemical formula (IV): MaRb (IV), Here, M is a metal, Each R is independent and can be H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, anionic ligand, neutral ligand, or polydentate ligand. A method for satisfying a≧1 and b≧1. [Form 21] A method according to Embodiment 20, wherein M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), tantalum (Ta), cesium (Cs), indium (In), molybdenum (Mo), or hafnium (Hf). [Form 22] A method according to Embodiment 2, wherein the developing step further comprises the step of developing in the presence of two or more different metal chelating agents. [Form 23] The method described in Embodiment 1, further, A method comprising the step of performing a post-exposure bake at a temperature of less than 180°C, following the step of providing the radiation-patterned film. [Form 24] The method according to Embodiment 1, the step of providing the radiation-patterned film further includes: A process of providing a patterned radiation-sensitive film as a resist film, A step of providing an exposure film having one or more radiation exposure regions, one or more radiation-exposed regions, and an interface region disposed between at least one of the radiation exposure regions and at least one of the radiation-exposed regions, or disposed within the radiation exposure region, by patterning the resist film by patterning radiation exposure. A method that includes [a certain feature]. [Form 25] A method according to Embodiment 24, wherein the patterned radiosensitive film is provided by spin coating. [Form 26] The method described in Embodiment 24, further, A method comprising a step of performing a post-coating bake at a temperature of less than 180°C prior to the patterning step. [Form 27] A method that utilizes registration, To provide a patterned radiation-sensitive film as a resist film, the process involves depositing a metal precursor onto the surface of a substrate, A step of providing an exposure film having one or more radiation exposure regions, one or more radiation-exposed regions, and an interface region disposed between at least one of the radiation exposure regions and at least one of the radiation-exposed regions, or disposed within the radiation exposure region, by patterning the resist film by patterning radiation exposure. A step of developing the exposure film in the presence of a metal chelating agent and a solvent to remove the interface region and either the radiation-exposed region or the radiation-unexposed region, thereby providing a pattern within the resist. A method that includes [a certain feature]. [Form 28] A method according to Embodiment 27, wherein the patterning radiation-sensitive film includes an extreme ultraviolet (EUV) sensitive film. [Form 29] A method according to Embodiment 28, wherein the patterning radiation exposure includes EUV exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum atmosphere. [Form 30] A method according to Embodiment 28, wherein the pattern comprises reduced line edge roughness (LER) compared to a pattern developed without the metal chelating agent. [Form 31] A method according to Embodiment 28, wherein the metal chelating agent is configured to preferentially remove the interface region, and the solvent is configured to preferentially remove either the radiation-exposed region or the non-radiation-exposed region. [Form 32] An apparatus for forming a resist film, A deposition module equipped with a chamber for depositing patterned radiosensitive films, A patterning module equipped with a photolithography tool having a radiation source with a wavelength of less than 300 nm, A developing module equipped with a chamber for developing the resist film, A controller comprising one or more memory devices, one or more processors, and system control software on which instructions are coded, Equipped with, The aforementioned instruction is, In the deposition module, a machine-readable command for depositing a metal precursor onto the upper surface of a semiconductor substrate in order to form the patterned radiation-sensitive film as a resist film, The patterning module provides a machine-readable command for forming an exposure film having one or more radiation exposure regions, one or more non-radiation exposure regions, and an interface region disposed between or within at least one of the radiation exposure regions and at least one of the non-radiation exposure regions, by directly patterning the resist film with a resolution of less than 300 nm using patterning radiation exposure. The developing module provides a machine-readable command for developing the exposure film in the presence of a metal chelating agent and a solvent to remove the interface region and at least one of the radiation-exposed region or the radiation-unexposed region, thereby providing a pattern within the resist film. A device including a device. [Form 33] The apparatus according to Embodiment 32, wherein the patterning radiation-sensitive film includes an extreme ultraviolet (EUV) sensitive film. [Form 34] The apparatus according to Embodiment 33, wherein the radiation source for the photolithography tool is a radiation source with a wavelength of less than 30 nm. [Form 35] The apparatus according to Embodiment 34, wherein the instruction including the machine-readable instruction further, Apparatus comprising a patterning module, which includes instructions for forming an exposure film having an EUV exposure region, an EUV non-exposure region, and an interface region disposed between or within the EUV exposure region, by directly patterning the resist film with a resolution of less than 30 nm by EUV exposure. [Form 36] The apparatus according to Embodiment 35, wherein the instruction including the machine-readable instruction further, Apparatus comprising a developing module, which includes an instruction for developing the exposure film in the presence of the metal chelating agent and the solvent to remove the interface region and at least one of the EUV exposure region or the EUV non-exposure region, thereby providing a pattern within the resist film.

Claims

1. A method for processing radiation-patterned films, A step of providing a radiation-patterned film having an interface region positioned between a radiation-exposed region and a non-radiation-exposed region, or positioned within a radiation-exposed region, wherein the interface region comprises a radiation-exposed metal center. A step of dry developing the radiation-patterned film in the presence of a metal chelating agent, wherein the metal chelating agent is configured to bond to the radiation-exposed metal centers in the interface region, A method that includes [a certain feature].

2. A method according to claim 1, wherein the radiation-patterned film includes an extreme ultraviolet (EUV) sensitive film.

3. A method according to claim 2, wherein the interface region includes a transition region located between at least one EUV exposure region and at least one EUV non-exposure region.

4. A method according to claim 2, wherein the dry developing step further includes a step of removing the interface region.

5. A method according to claim 2, wherein the metal chelating agent preferentially bonds to the radiation-exposed metal centers in the interface region compared to the metal centers present in the non-radiation-exposed region.

6. A method according to claim 2, wherein the radiation-exposed metal center comprises a transition metal.

7. A method according to claim 2, wherein the radiation-exposed metal center comprises tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), or tantalum (Ta).

8. A method according to claim 2, wherein the radiation-patterned film comprises a metal oxide film or an organometallic oxide film.

9. The method according to claim 8, wherein the radiation-patterned film is formed from a metal precursor having a structure having the following chemical formula (IV): MaRb (IV), Here, M is a metal, Each R is independent and can be H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, anionic ligand, neutral ligand, or polydentate ligand. A method where a ≥ 1 and b ≥ 1.

10. A method according to claim 9, wherein M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), tantalum (Ta), cesium (Cs), indium (In), molybdenum (Mo), or hafnium (Hf).

11. A method according to claim 2, wherein the dry developing step further comprises a step of dry developing in the presence of two or more different metal chelating agents.

12. The method according to claim 1, further, A method comprising the step of performing a post-exposure bake at a temperature of less than 180°C, following the step of providing the radiation-patterned film.

13. The method according to claim 1, wherein the step of providing the radiation-patterned film is further: A process of providing a patterned radiation-sensitive film as a resist film, A step of providing an exposure film having one or more radiation exposure regions, one or more radiation-exposed regions, and an interface region disposed between at least one of the radiation exposure regions and at least one of the radiation-exposed regions, or disposed within the radiation exposure region, by patterning the resist film by patterning radiation exposure. A method that includes [a certain feature].

14. A method according to claim 13, wherein the patterned radiation-sensitive film is provided by spin coating.

15. The method according to claim 13, further, A method comprising a step of performing a post-coating bake at a temperature of less than 180°C prior to the patterning step.

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