Tin Precursors for EUV Dry Resist Deposition

Abstract

The present disclosure relates to a precursor composition for forming an irradiation-sensitive film. In particular, the present disclosure is directed to the use of a metal-containing precursor having a haloaliphatic substitution component or an unsaturated substitution component, or having other reactive sites, which advantageously reacts in the presence of extreme ultraviolet exposure to form a resist film having improved etching resistance and / or reduced shrinkage during processing. Alternatively, by using a metal-containing precursor having a haloaliphatic substitution component or an unsaturated substitution component, or having other reactive sites, to pattern a structure having a carbon-containing underlayer, it may advantageously react with the underlayer to enhance the adhesion between the resist film and the underlayer.

Description

Technical Field

[0001] [Incorporation by Reference] The PCT application form is submitted simultaneously with this specification as part of this application. Each application identified in the simultaneously submitted PCT application form and for which this application claims benefit or priority is hereby incorporated by reference in its entirety for all purposes.

[0002] This disclosure generally relates to the field of semiconductor processing, and more particularly to extreme ultraviolet (EUV) photoresist (PR) lithography technology and materials.

Background Art

[0003] The background description provided herein is for the purpose of generally presenting the content of the present technology. Within the scope described in this background art section, research by the inventors named at the present time, as well as aspects of the description that cannot be separately regarded as prior art at the time of filing, are not recognized as prior art against the present technology, whether explicitly or implicitly.

[0004] Patterning of thin films in semiconductor processing is often an important step in semiconductor manufacturing. Patterning involves lithography. In conventional photolithography, such as 193 nm photolithography, photons are emitted from a photon source onto a mask and a pattern is printed onto a photosensitive photoresist, thereby causing a chemical reaction in the photoresist. By the chemical reaction, specific portions of the photoresist are removed after development to form a pattern.

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

[0006] Extreme ultraviolet (EUV) lithography can extend lithography technology by moving to imaging source wavelengths shorter than those achievable with conventional photolithography methods. EUV light sources with wavelengths of about 10-20 nm or 11-14 nm (e.g., a wavelength of 13.5 nm) can be used in state-of-the-art lithography tools, also called scanners. Since EUV radiation is strongly absorbed by a wide range of solid and fluid materials, including quartz, air, and water vapor, it operates in a vacuum.

SUMMARY OF THE INVENTION

[0007] The present disclosure relates to a precursor composition for forming an irradiation-sensitive film. In particular, the present disclosure is directed to the use of a metal-containing precursor having a haloaliphatic substitution component or an unsaturated substitution component, or other reactive sites, which advantageously reacts in the presence of extreme ultraviolet exposure to form a resist film with improved etching resistance and / or reduced shrinkage during processing. Alternatively, a metal-containing precursor having a haloaliphatic substitution component or an unsaturated substitution component, or other reactive sites, may be used to pattern a structure having a carbon-containing underlayer, thereby advantageously reacting with the underlayer to enhance the adhesion between the resist film and the underlayer.

[0008] Furthermore, by using such a precursor, shrinkage of the film during radiation exposure or post-exposure baking can be reduced. For example, when exposed to radiation and / or heat, such substituents on the precursor typically cleave or react, thereby increasing the contrast in material properties between the exposed and unexposed regions. Cleavage of such groups can create voids within the film, which may result in radiation- and bake-induced shrinkage. Accordingly, the present disclosure encompasses the use of precursors to provide a film that has enhanced radiation sensitivity, improved patterning quality (e.g., having improved line width roughness (LWR) and / or line edge roughness (LER)), increased film density, reduced dose-to-size (DtS), and / or minimized film shrinkage when exposed to radiation, heat, or other post-patterning processes (e.g., etching).

[0009] Accordingly, in a first aspect, the present invention encompasses a precursor composition for forming an irradiation-sensitive resist film. In some embodiments, the composition is a precursor of the formula M(R 1 )4, wherein M is a metal such as lead, germanium, tin, and hafnium, and R 1 are each independently aliphatic, alkylsilyl, amino, amido, azido, cyano, alkylcarbonyl, isocyanato, isothiocyanato, thiocyanato, alkoxy, heterocyclyl, aryl, alkenyl, alkynyl, or the R 1 substituent components may be linked to form a ring, and the precursor includes at least one R 1 that is an unsaturated substituent component, and when M is tin and the R 1 are the same, R 1 is alkynyl, the precursor forms a metal-oxo network primary film having an unsaturated substituent component after deposition on a substrate, and when the unsaturated substituent component in the metal-oxo network primary film is exposed to radiation, a hydrocarbon secondary network is formed.

[0010] In some embodiments, the hydrocarbon secondary network increases the etch resistance.

[0011] In some embodiments, the hydrocarbon secondary network reduces the film shrinkage after patterning.

[0012] In some embodiments, M is tin and the composition contains less than 0.5% of a tin-containing compound comprising two aliphatic R 1 substituent components.

[0013] In a second aspect, the present invention encompasses a method for processing a semiconductor substrate. In some embodiments, the method comprises a precursor of formula M(R 1 )4 in the presence of water, wherein M is a metal such as lead, germanium, tin, and hafnium, and R 1 are each independently an aliphatic, alkylsilyl, amino, amide, azide, cyano, alkylcarbonyl, isocyanato, isothiocyanato, thiocyanato, alkoxy, heterocyclyl, aryl, alkenyl, or alkynyl, or the R 1 substituent components may be linked to form a ring, and at least one R 1 is an unsaturated substituent component, depositing the precursor on a substrate under the condition that when M is tin and the Rs 1 are the same, R 1 is alkynyl, to form an irradiation-sensitive metal-oxo network resist film, patterning the metal-oxo network resist film having an unsaturated substituent component by extreme ultraviolet exposure to form a photopatterned metal-oxo network resist film, and forming a photopatterned and crosslinked metal-oxo network resist film by forming a hydrocarbon secondary network when the unsaturated substituent component in the metal-oxo network resist film is exposed to radiation.

[0014] In some embodiments, the method includes forming a resist mask by dry-developing a photopatterned and crosslinked metal-oxo network resist film.

[0015] In some embodiments, the hydrocarbon secondary network increases etch resistance.

[0016] In some embodiments, the hydrocarbon secondary network reduces post-patterning film shrinkage.

[0017] In some embodiments, M is tin.

[0018] In some embodiments, the precursor has the structure of formula (I).

Chemical formula

[0019] In some embodiments, each L is NR 3 R 4 .

[0020] In some embodiments, L is dimethylamino, tert-butylamino, diethylamino, ethylmethylamino, methylpropylamino, pyrrolidino, or piperidino.

[0021] In some embodiments, each L is OR 5 .

[0022] In some embodiments, L is methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, or n-butoxy.

[0023] In some embodiments, the unsaturated substitution component is C2-C6 alkenyl, C2-C6 branched alkenyl, or C2-C6 alkynyl.

[0024] In some embodiments, the unsaturated substitution component is C5-C6 alkenyl, C5-C6 branched alkenyl, or C5-C6 alkynyl.

[0025] In some embodiments, the precursor is vinyltri(methoxy)tin, vinyltri(ethoxy)tin, vinyltri(isopropoxy)tin, vinyltri(tert-butoxy)tin, vinyltris(dimethylamino)tin, vinyltris(pyrrolidino)tin, 2-propenyltri(isopropoxy)tin, 2-propenyltri(tert-butoxy)tin, 2-propenyltris(dimethylamino)tin, 2-propenyltris(pyrrolidino)tin, 2-methyl-1-propenyltri(isopropoxy)tin, 2-methyl-1-propenyltri(tert-butoxy)tin, 2-methyl-1-propenyltris(dimethylamino)tin, 2-propenyltris(pyrrolidino)tin, vinyltri(1-propynyl)tin, isopropenyltris(1-propynyl)tin, isopropenyltris(dimethylamino)tin, 2-methyl-1-propenyltri(1-propynyl)tin, allyltri(isopropoxy)tin, allyltri(tert-butoxy)tin, allyltris(dimethylamino)tin, allyltris(pyrrolidino)tin, allyltri(1-propynyl)tin, 1-methylallyltri(isopropoxy)tin, 1-methylallyltri(tert-butoxy)tin, 1-methylallyltris(dimethylamino)tin, 1-methylallyltris(pyrrolidino)tin, or 1-methylallyltri(1-propynyl)tin.

[0026] In some embodiments, the deposition also includes providing a gradient film by including a tin-containing second precursor for forming the upper portion of the film.

[0027] In some embodiments, the deposition also includes providing a counter-reagent.

[0028] In some embodiments, the counter-reagent is water vapor.

[0029] In some embodiments, the resist film is an extreme ultraviolet-sensitive film.

[0030] In some embodiments, the resist film is organotin oxide, organotin hydroxide, halo organotin oxide, or halo organotin hydroxide.

[0031] In some embodiments, the method also includes providing an exposed film having a radiation-exposed area and a radiation-unexposed area by patterning the resist film by exposure to patterned radiation, and developing the exposed film to remove the radiation-exposed area to provide a pattern in a positive-tone resist film, or removing the radiation-unexposed area to provide a pattern in a negative-tone resist.

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

[0033] In some embodiments, the development is dry development or wet development.

[0034] In a third aspect, the present invention includes a precursor composition for forming an irradiation-sensitive resist film. In some embodiments, the composition is a precursor of the formula M(R 6 )4, wherein M is a metal such as lead, germanium, tin, or hafnium, and R 6is independently, aliphatic, alkylsilyl, amino, amide, alkoxy, heterocyclyl, haloaliphatic, aryl, or R 6 substituent components may be linked to form a ring, and at least one R 6 comprises a precursor, wherein the precursor forms a metal-oxo network resist film having a halo-containing substituent component, and the halo-containing substituent component forms a metal-halo bond when exposed to radiation.

[0035] In some embodiments, the metal-halo bond increases the etching resistance of the metal-oxo network resist film.

[0036] In some embodiments, the metal-halo bond reduces the shrinkage of the metal-oxo network resist film.

[0037] In some embodiments, M is tin and the composition contains less than 0.5% of a tin-containing compound containing two aliphatic R 6 substituent components.

[0038] In a fourth aspect, the present invention encompasses a method for processing a semiconductor substrate. In some embodiments, the method comprises a precursor of formula M(R 6 )4 in the presence of water, wherein M is a metal such as lead, germanium, tin, and hafnium, and R 6 is independently, aliphatic, alkylsilyl, amino, amide, azide, cyano, alkylcarbonyl, isothiocyanato, thiocyanato, alkoxy, heterocyclyl, haloaliphatic, aryl, or R 6 substituent components may be linked to form a ring, and at least one R 6Depositing a precursor that is a halo-containing substitution component on a substrate to form an irradiation-sensitive metal-oxo network resist film having a halo-containing substitution component, and patterning the irradiation-sensitive metal-oxo network resist film having a halo-containing substitution component by extreme ultraviolet exposure to form a photopatterned metal-halo bond-containing metal-oxo network resist film.

[0039] In some embodiments, the method also includes forming a resist mask by dry developing the photopatterned metal-halide bond-containing metal-oxo network resist film.

[0040] In some embodiments, M is tin.

[0041] In some embodiments, the halo-containing substitution component is a β-halo-containing substitution component.

[0042] In some embodiments, the precursor includes the structure of formula (II). [Chemical formula] (In the formula, R 7 is C 2-6 haloaliphatic, L is each independently NR 8 R 9 or OR 10 and R 8 R 9 and R 10 are each independently hydrogen, alkylcarbonyl, or aliphatic, and R 8 substitution component and R 9 substitution component may be linked to form a ring.)

[0043] In some embodiments, each L is NR 8 R 9 .

[0044] In some embodiments, L is dimethylamino, tert-butylamino, diethylamino, ethylmethylamino, methylpropylamino, pyrrolidino, or piperidino.

[0045] In some embodiments, L is each OR 10 is.

[0046] In some embodiments, L is methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, sec-butoxy, or n-butoxy.

[0047] In some embodiments, R 7 is C5-C6 haloaliphatic.

[0048] In some embodiments, the halo of the halo-containing substitution component is at least one fluorine or iodine.

[0049] In some embodiments, the precursor is 2-fluoroethyltris(dimethylamino)tin, 2-fluoroethyltris(t-butoxy)tin, 2,2-difluoroethyltris(dimethylamino)tin, 2,2-difluoroethyltris(t-butoxy)tin, 2,2,2-trifluoroethyltris(dimethylamino)tin, or 2,2,2-trifluoroethyltris(t-butoxy)tin.

[0050] In some embodiments, the deposition also includes providing a gradient film by including a tin-containing second precursor for forming the upper part of the film.

[0051] In some embodiments, the deposition also includes providing a counter-reactant.

[0052] In some embodiments, the counter-reactant is water vapor.

[0053] In some embodiments, the resist film is an extreme ultraviolet sensitive film.

[0054] In some embodiments, the resist film is organotin oxide, organotin hydroxide, organotin oxide hydroxide, halo organotin oxide, halo organotin hydroxide, or halo organotin oxide hydroxide.

[0055] In some embodiments, the method also provides an exposed film having a radiation-exposed area and a non-radiation-exposed area by patterning the resist film by exposure to patterned radiation, and removing the radiation-exposed area by developing the exposed film to provide a pattern in the positive-tone resist film, or removing the non-radiation-exposed area to provide a pattern in the negative-tone resist.

[0056] In some embodiments, the patterning is EUV exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum atmosphere.

[0057] In some embodiments, the development is dry development or wet development.

[0058] In a fifth aspect, the present disclosure includes a method of creating a patterning structure. In some embodiments, the method includes depositing a carbon-containing underlayer on a substrate and depositing a tin precursor under conditions that promote the formation of unsaturated carbon-carbon bonds in the carbon-containing underlayer to form an irradiation-sensitive tin-oxo network resist film on the carbon-containing underlayer, whereby the formation of unsaturated carbon-carbon bonds enhances the adhesion of the resist film to the underlayer.

[0059] In some embodiments, the increased adhesion reduces line width roughness.

[0060] In some embodiments, the increased adhesion reduces the dose for size.

[0061] In some embodiments, the increased adhesion reduces line edge roughness.

[0062] In some embodiments, the tin precursor has the structure of formula (I). [Chemical formula] (Wherein, R 2 is C 2-6 aliphatic, and each L is independently NR 3 R 4 or OR 5 , and each of R 3 , R 4 , and R 5 is independently hydrogen, alkylcarbonyl, or aliphatic, and the R 3 substituent and the R 4 substituent may be linked to form a ring.)

[0063] In some embodiments, each L is NR 3 R 4 .

[0064] In some embodiments, L is dimethylamino, tert-butylamino, diethylamino, ethylmethylamino, methylpropylamino, pyrrolidino, or piperidino.

[0065] In some embodiments, each L is OR 5 .

[0066] In some embodiments, L is methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, or n-butoxy.

[0067] In some embodiments, the unsaturated substituent is C2-C6 aliphatic.

[0068] In some embodiments, the unsaturated substituent is C2-C6 alkenyl, C2-C6 branched alkenyl, or C2-C6 alkynyl.

[0069] In some embodiments, the unsaturated substitution component is C5-C6 alkenyl, C5-C6 branched alkenyl, or C5-C6 alkynyl.

[0070] In some embodiments, the tin precursor is vinyltri(methoxy)tin, vinyltri(ethoxy)tin, vinyltri(isopropoxy)tin, vinyltri(tert-butoxy)tin, vinyltris(dimethylamino)tin, vinyltris(pyrrolidino)tin, 2-propenyltri(isopropoxy)tin, 2-propenyltri(tert-butoxy)tin, 2-propenyltris(dimethylamino)tin, 2-propenyltris(pyrrolidino)tin, 2-methyl-1-propenyltri(isopropoxy)tin, 2-methyl-1-propenyltri(tert-butoxy)tin, 2-methyl-1-propenyltris(dimethylamino)tin, 2-propenyltris(pyrrolidino)tin, vinyltri(1-propynyl)tin, isopropenyltri(1-propynyl)tin, isopropenyltris(dimethylamino)tin, 2-methyl-1-propenyltri(1-propynyl)tin, allyltri(isopropoxy)tin, allyltri(tert-butoxy)tin, allyltris(dimethylamino)tin, allyltris(pyrrolidino)tin, allyltri(1-propynyl)tin, 1-methylallyltri(isopropoxy)tin, 1-methylallyltri(tert-butoxy)tin, 1-methylallyltris(dimethylamino)tin, 1-methylallyltris(pyrrolidino)tin, or 1-methylallyltri(1-propynyl)tin.

[0071] In some embodiments, the deposition also includes providing a tin-containing second precursor for forming the upper portion of the film to provide a gradient film.

[0072] In some embodiments, the deposition also includes providing a counter-reactant.

[0073] In some embodiments, the counter-reactant is water vapor.

[0074] In some embodiments, the resist film is an extreme ultraviolet sensitive film.

[0075] In some embodiments, the resist film is organotin oxide, organotin hydroxide, organotin oxide hydroxide, halo organotin oxide, halo organotin hydroxide, or halo organotin oxide hydroxide.

[0076] In some embodiments, the method also provides an exposed film having a radiation exposure area and a non-exposed radiation area by patterning the resist film by exposure to patterned radiation, and removing the radiation exposure area by developing the exposed film to provide a pattern in the positive tone resist film, or removing the non-exposed radiation area to provide a pattern in the negative tone resist.

[0077] In some embodiments, the patterning is EUV exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum atmosphere.

[0078] In some embodiments, the development is dry development or wet development.

[0079] In a sixth aspect, the invention includes a method of creating a patterning structure. In some embodiments, the method includes depositing a carbon-containing underlayer having a surface on a substrate, and depositing a tin precursor under conditions to form a tin-halo bond on the surface of the carbon-containing underlayer to form an irradiation-sensitive tin-oxo network resist film on the carbon-containing underlayer, whereby the tin-halo bond on the surface of the carbon-containing underlayer increases the etching resistance of the resist film.

[0080] In some embodiments, the tin precursor has the structure of formula (II).

Chemical formula

[0081] In some embodiments, each L is NR 8 R 9 .

[0082] In some embodiments, L is dimethylamino, tert-butylamino, diethylamino, ethylmethylamino, methylpropylamino, pyrrolidino, or piperidino.

[0083] In some embodiments, each L is OR 10 .

[0084] In some embodiments, L is methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, sec-butoxy, or n-butoxy.

[0085] In some embodiments, R 7 is a C5-C6 haloaliphatic.

[0086] In some embodiments, the halo of the halo-containing substituent is at least one fluorine or iodine.

[0087] In some embodiments, the tin precursor is 2-fluoroethyltris(dimethylamino)tin, 2-fluoroethyltris(t-butoxy)tin, 2,2-difluoroethyltris(dimethylamino)tin, 2,2-difluoroethyltris(t-butoxy)tin, 2,2,2-trifluoroethyltris(dimethylamino)tin or 2,2,2-trifluoroethyltris(t-butoxy)tin.

[0088] In some embodiments, the increased etch resistance reduces the dosage relative to the size.

[0089] In some embodiments, the deposition also includes providing a gradient film by including a tin-containing second precursor for forming the upper part of the film.

[0090] In some embodiments, the deposition also includes providing a counter-reactant.

[0091] In some embodiments, the counter-reactant is water vapor.

[0092] In some embodiments, the resist film is an extreme ultraviolet-sensitive film.

[0093] In some embodiments, the resist film is organotin oxide, organotin hydroxide, organotin oxide hydroxide, halo organotin oxide, halo organotin hydroxide, or halo organotin oxide hydroxide.

[0094] In some embodiments, the method also includes patterning the resist film by exposure to patterned radiation to provide an exposed film having a radiation-exposed area and a radiation-unexposed area, and developing the exposed film to remove the radiation-exposed area to provide a pattern in a positive-tone resist film or removing the radiation-unexposed area to provide a pattern in a negative-tone resist.

[0095] In some embodiments, the patterning is EUV exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum atmosphere.

[0096] In some embodiments, the development is dry development or wet development.

[0097] In a seventh aspect, the invention includes a patterned radiation sensitive film. In some embodiments, the film comprises an organometallic-oxo material, the material comprising a metal, oxygen, and an alkylsilyl, heterocyclyl, or aryl.

[0098] In some embodiments, the alkylsilyl is trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, ethyldimethylsilyl, or triisopropylsilyl.

[0099] In some embodiments, the aryl is phenyl, benzyl, or methylcyclopentadienyl.

[0100] In some embodiments, the heterocyclyl is imidazolyl, pyrrolidinyl, pyridinyl, tetrahydrofuranyl, tetrahydropyranyl, or dioxanyl.

[0101] In some embodiments, the organometallic-oxo material has a network of metal-oxygen bonds and metal-alkylsilyl or metal-heterocyclyl bonds.

[0102] In some embodiments, the patterned radiation sensitive film is an extreme ultraviolet sensitive film.

[0103] In some embodiments, the metal is tin.

[0104] In an eighth aspect, the invention includes a patterned radiation sensitive film. In some embodiments, the film comprises an organotin-oxo material, the organotin-oxo material comprising tin, oxygen, and a C 5-6 aliphatic or a C 5-6 haloaliphatic.

[0105] In some embodiments, the C 5-6 haloaliphatic is a C 5-6 haloalkyl, a C 5-6 haloalkenyl, or a C 5-6 haloalkynyl.

[0106] In some embodiments, C 5-6 The haloaliphatic is one or more halo substitution components.

[0107] In some embodiments, C 5-6 The aliphatic is pentyl, pentenyl, pentynyl, hexyl, hexenyl, or hexynyl.

[0108] In some embodiments, C 5-6 The aliphatic is cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, or cyclohexadienyl.

[0109] In some embodiments, the material is a network of tin-oxygen bonds and tin-C 5-6 aliphatic bonds or tin-C 5-6 haloaliphatic bonds.

[0110] In a ninth aspect, the invention includes a precursor composition for forming an irradiation-sensitive resist film. In some embodiments, the composition includes a tin precursor of formula (III) or formula (IV). [Chemical formula] (In the formula, R 11 is alkylsilyl, amino, amide, alkoxy, heterocyclyl, aryl, C 5-6 aliphatic substitution component or C 5-6 haloaliphatic substitution component, or R 11 substitution components may be linked to form a ring, L is independently NR 12 R 13 or OR 14 and R 12 , R 13 , and R 14 are each independently hydrogen, alkylcarbonyl, or aliphatic, and R 12 and R 13The replacement components may be linked to form a ring. After the precursor is deposited on the substrate, it forms a tin-oxo primary network film, and when the tin-oxo primary network film is exposed to radiation, a hydrocarbon secondary network is formed.)

[0111] In some embodiments, the hydrocarbon secondary network increases the etching resistance.

[0112] In some embodiments, the hydrocarbon secondary network reduces the film shrinkage after patterning.

[0113] In some embodiments, each L is NR 12 R 13 and is.

[0114] In some embodiments, L is dimethylamino, tert-butylamino, diethylamino, ethylmethylamino, methylpropylamino, pyrrolidino, or piperidino.

[0115] In some embodiments, the tin precursor has the structure of formula (III), and each L is OR 14 and is.

[0116] In some embodiments, L is methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, sec-butoxy, or n-butoxy.

[0117] In a tenth aspect, the present invention includes a method of employing a resist. In some embodiments, the method includes providing a tin-containing resist film by depositing a tin-containing precursor on the surface of a substrate, and the tin-containing precursor includes the structure of formula (III) or (IV).

Chemical formula

[0118] In some embodiments, each L is NR 12 R 13 Is.)

[0119] In some embodiments, L is dimethylamino, tert-butylamino, diethylamino, ethylmethylamino, methylpropylamino, pyrrolidino, or piperidino.)

[0120] In some embodiments, the tin precursor has the structure of formula (III), and each L is OR 14 Is.)

[0121] In some embodiments, L is methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, sec-butoxy, or n-butoxy.)

[0122] In some embodiments, the deposition also includes providing a gradient film by including a tin-containing second precursor for forming the upper part of the film.)

[0123] In some embodiments, the deposition also includes providing a counter-reagent.)

[0124] In some embodiments, the counter-reagent is water vapor.)

[0125] In some embodiments, the tin oxide resist film is an extreme ultraviolet sensitive film.)

[0126] In some embodiments, the tin oxide resist film is organotin oxy, organotin oxide, organotin oxide hydroxide, halo organotin oxy, halo organotin oxide, or halo organotin oxide hydroxide.

[0127] In an eleventh aspect, the present invention encompasses a precursor composition for forming an irradiation-sensitive resist film. In some embodiments, the composition comprises a precursor of formula (V), (VI), or (VII). [Chemical formula] (Wherein R 15 is (C(R 17 )2) n and R 17 are each independently hydrogen or aliphatic, or the R 17 substituent components may be linked to form a ring, n is an integer from 1 to 10, and R 16 are each independently alkylsilyl, amino, heterocyclyl, aryl, C 5-6 aliphatic or C 5-6 haloaliphatic, or the R 7 substituent components may be linked to form a ring, L is each independently NR 17 R 18 or OR 19 and R 17 , R 18 , and R 19 are each independently hydrogen or aliphatic, or the R 17 and R 18 substituent components may be linked to form a ring, and the precursor forms a tin-oxo primary network film after deposition on a substrate, and a hydrocarbon secondary network is formed when the tin-oxo primary network film is exposed to radiation.)

[0128] In some embodiments, the hydrocarbon secondary network increases the etching resistance.

[0129] In some embodiments, the hydrocarbon secondary network reduces post-patterning film shrinkage.

[0130] In some embodiments, each L is NR 17 R 18 and is.

[0131] In some embodiments, L is dimethylamino, tert-butylamino, diethylamino, ethylmethylamino, methylpropylamino, pyrrolidino, or piperidino.

[0132] In some embodiments, each L is OR 19 and is.

[0133] In some embodiments, L is methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, sec-butoxy, or n-butoxy.

[0134] In a twelfth aspect, the present invention includes a method of employing a resist. In some embodiments, the method includes providing a tin oxide resist film by depositing a tin-containing precursor on the surface of a substrate, the tin-containing precursor including a structure of formula (V), (VI), or (VII).

Chemical formula

[0135] In some embodiments, each L is NR 17 R 18 .

[0136] In some embodiments, L is dimethylamino, tert-butylamino, diethylamino, ethylmethylamino, methylpropylamino, pyrrolidino, or piperidino.

[0137] In some embodiments, each L is OR 19 .

[0138] In some embodiments, L is methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, sec-butoxy, or n-butoxy.

[0139] In some embodiments, the deposition also includes providing a gradient film by including a tin-containing second precursor for forming the upper part of the film.

[0140] In some embodiments, the deposition also includes providing a counter-reagent.

[0141] In some embodiments, the counter-reagent is water vapor.

[0142] In some embodiments, the resist film is an extreme ultraviolet sensitive film.

[0143] In some embodiments, the tin oxide resist film is organotin oxy, organotin oxide, organotin oxide hydroxide, halo organotin oxy, halo organotin oxide, or halo organotin oxide hydroxide.

[0144] In some embodiments, the method also provides an exposed film having a radiation-exposed area and a non-radiation-exposed area by patterning a resist film by exposure to patterned radiation, and removing the radiation-exposed area by developing the exposed film to provide a pattern in a positive-tone resist film, or removing the non-radiation-exposed area to provide a pattern in a negative-tone resist.

[0145] In some embodiments, the patterning is EUV exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum atmosphere.

[0146] In some embodiments, the development is dry development or wet development.

[0147] In some embodiments, dry development is employed for an exposed film containing tin bonded to a fluorine atom or an iodine atom.

[0148] In a 13th aspect, the present invention includes a method of depositing a tin oxide resist film on a surface of a substrate, the method including reacting a tin compound with acetamide or alcohol to form a tin precursor containing Sn(NR 20 R 21 )4 or Sn2(NR 20 R 21 )4 (wherein R 20 and R 21 are each independently hydrogen or aliphatic, or R 20 and R 21 substituent components may be linked to form a ring), depositing the tin precursor on the surface of the substrate, exposing the tin precursor on the surface of the substrate to extreme ultraviolet rays, and forming a tin oxide resist film.

[0149] In some embodiments, the acetamide is acetamide, N-methylacetamide, N-ethylacetamide, N-methylformamide, N-ethylformamide, M-methylpropionamide, or propanamide.

[0150] In some embodiments, the alcohol is methanol, ethanol, butanol, t-butanol, isopropanol, or propanol.

[0151] In some embodiments, R 20 and R 21 are each independently aliphatic.

[0152] In some embodiments, the tin compound is tetrakis(dimethylamino)tin or bis(dimethylamino)tin(II) dimer.

[0153] In a fourteenth aspect, the invention includes an apparatus for forming a resist film. In some embodiments, the apparatus includes a deposition module including a chamber for depositing an irradiation-sensitive resist film, one or more memory devices, one or more processors, and system control software encoded with instructions including machine-readable instructions for depositing a metal-containing precursor and an optional ligand-containing precursor on an upper surface of a semiconductor substrate to form a resist film in the deposition module, and a controller including the system control software, wherein the resist film includes a metal, oxygen, and alkylsilyl, heterocyclyl, or aryl.

[0154] In some embodiments, the resist film includes an extreme ultraviolet-sensitive film.

[0155] In some embodiments, the apparatus also includes a patterning module that includes a photolithography tool having a radiation source with a wavelength of less than 300 nm, and the instructions including machine-readable instructions further include instructions for forming an exposed film having an exposed radiation range and an unexposed radiation range by directly patterning a resist film at a resolution of less than 300 nm by patterning radiation exposure in the patterning module.

[0156] In some embodiments, the source of the photolithography tool is a source of radiation with a wavelength of less than 30 nm.

[0157] In any of the embodiments herein, the deposition includes providing a metal-containing precursor in vapor form. In other embodiments, the deposition includes providing a metal-containing precursor, a ligand-containing precursor, and / or a co-reactant in vapor form. Non-limiting deposition processes include chemical vapor deposition (CVD), atomic layer deposition (ALD), and molecular layer deposition (MLD), as well as plasma-excited forms thereof.

[0158] In any of the embodiments herein, the deposition further includes providing a co-reactant. Non-limiting co-reactants include oxygen-containing precursors or chalcogenide-containing precursors, and any of those described herein (e.g., oxygen-containing co-reactants such as oxygen (O2), ozone (O3), water, peroxides, hydrogen peroxide, oxygen plasma, water plasma, alcohols, dihydroxy alcohols, polyhydroxy alcohols, fluorinated dihydroxy alcohols, fluorinated polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl sites, and combinations thereof). Further details are described below.

[0159] Definitions "Aliphatic" means having at least 1 to 50 carbon atoms (C 1-50 ), e.g., 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10) is a hydrocarbon moiety having, and including saturated groups such as alkanes (or alkyls) and unsaturated groups such as alkenes (or alkenyls), alkynes (or alkynyls), and further including their cyclic versions, and further including straight-chain and branched-chain configurations, as well as all stereoisomers and positional isomers. Such hydrocarbons can be unsubstituted or can be substituted with one or more groups such as those described herein for halogen or alkyl groups.

[0160] What "alkenyl" means is an optionally substituted C having one or more double bonds 2-24 alkyl group. An alkenyl group can be cyclic (e.g., C 3-24 cycloalkenyl) or acyclic. An alkenyl group can also be substituted or unsubstituted. For example, an alkenyl group can be substituted with one or more substituents as described herein for alkyl. Non-limiting unsubstituted alkenyl groups include C 2-8 alkenyl, C 2-6 alkenyl, C 2-5 alkenyl, C 2-4 alkenyl, or C 2-3 alkenyl. Exemplary non-limiting alkenyl groups include vinyl or ethenyl (-CH=CH2), 1-propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (e.g., -CH2CH2CH=CH2), 2-butenylidene (e.g., =CH-CH=CHCH3), etc.

[0161] What "alkenylene" means is the polyvalent (e.g., divalent) form of an alkenyl group, which is an optionally substituted C having one or more double bonds 2-24 alkyl group. An alkenylene group can be cyclic (e.g., C 3-24It can be cycloalkenyl or acyclic. The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substituents as described for alkyl herein. Exemplary non-limiting alkenylene groups include -CH=CH- or -CH=CHCH2-.

[0162] "Alkoxy" means -OR, where R is an optionally substituted alkyl group as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, trihaloalkoxy (such as trifluoromethoxy), etc. The alkoxy group can be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substituents as described for alkyl herein. Exemplary unsubstituted alkoxy groups include C 1-3 、C 1-6 、C 1-12 、C 1-16 、C 1-18 、C 1-20 、or C 1-24 alkoxy groups.

[0163] "Alkyl" and the prefix "alk" mean a branched or unbranched saturated hydrocarbon group having 1 to 24 carbon atoms, for example, methyl (Me), ethyl (Et), n-propyl (n-Pr or nPr), isopropyl (i-Pr or iPr), cyclopropyl, n-butyl (n-Bu or nBu), isobutyl (i-Bu or iBu), s-butyl (s-Bu or sBu), t-butyl (t-Bu or tBu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group can be cyclic (e.g., C 3-24It can be cycloalkyl or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can include haloalkyl in which the alkyl group is substituted with one or more halo groups as described herein. In another example, the alkyl group can be substituted with one, two, three, or in the case of an alkyl group having 2 or more carbons, four substitution components independently selected from the group consisting of: (1) C 1-6 alkoxy (e.g., -O-Ak, where Ak is optionally substituted C 1-6 alkyl); (2) amino (e.g., -NR N1 R N2 where R N1 and R N2 are each independently H or optionally substituted alkyl, or R N1 and R N2 together with the nitrogen atom to which each is attached form a heterocyclyl group); (3) aryl; (4) arylalkoxy (e.g., -O-Lk-Ar, where Lk is a divalent form of optionally substituted alkyl and Ar is optionally substituted aryl); (5) aroyl (e.g., -C(O)-Ar, where Ar is optionally substituted aryl); (6) cyano (e.g., -CN); (7) carboxaldehyde (e.g., -C(O)H); (8) carboxyl (e.g., -CO2H); (9) C 3-8 cycloalkyl (e.g., a monovalent saturated or unsaturated non-aromatic cyclic C 3-8hydrocarbon group); (10) halo (e.g., F, Cl, Br, or I); (11) heterocyclyl (e.g., a three-membered, four-membered, five-membered, six-membered, or seven-membered ring containing one, two, three, or four non-carbon heteroatoms such as nitrogen, oxygen, phosphorus, sulfur, or halo, unless otherwise specified); (12) heterocyclyloxy (e.g., -O-Het, where Het is heterocyclyl as described herein); (13) heterocyclyloyl (e.g., -C(O)-Het, where Het is heterocyclyl as described herein); (14) hydroxyl (e.g., -OH); (15) N-protected amino; (16) nitro (e.g., -NO2); (17) oxo (e.g., =O); (18) -CO2R A wherein R A is selected from the group consisting of (a) C 1-6 alkyl, (b) C 4-18 aryl, and (c) (C 4-18 aryl)C 1-6 alkyl (e.g., -Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (19) -C(O)NR B R C wherein R B and R C are each independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) (C 4-18 aryl)C 1-6 alkyl (e.g., -Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); and (20) -NR G R H wherein R G and R H are each independently selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C 1-6 alkyl, (d) C 2-6 alkenyl (e.g., an optionally substituted alkyl having one or more double bonds), (e) C 2-6Alkynyl (e.g., optionally substituted alkyl having one or more triple bonds), (f) C 4-18 Aryl, (g) (C 4-18 Aryl)C 1-6 Alkyl (e.g., Lk - Ar, where Lk is 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 as described herein and Cy is an optionally substituted cycloalkyl), selected from the group consisting of, and in one embodiment, there are no two groups 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 1-2 、C 1-3 、C 1-6 、C 1-12 、C 1-16 、C 1-18 、C 1-20 、C 1-24 、C 2-3 、C 2-6 、C 2-12 、C 2-16 、C 2-18 、C 2-20 、or C 2-24 alkyl group.

[0164] "Alkylene" means, as described herein, the polyvalent (e.g., divalent) form of an alkyl group. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is C 1-3 、C 1-6 、C 1-12 、C 1-16 、C 1-18 、C 1-20 、C 1-24 、C 2-3 、C 2-6, C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 is an alkylene group. The alkylene group can be branched or unbranched. The alkylene group can also be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more substituents as described herein for alkyl.

[0165] "Alkylcarbonyl" means an alkyl group as defined above attached to the parent molecular moiety through a carbonyl group. Exemplary non-limiting alkylcarbonyl groups include methylcarbonyl, ethylcarbonyl, and isopropylcarbonyl among others.

[0166] "Alkynyl" means an optionally substituted C 2-24 alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic, and examples include ethynyl, 1-propynyl, etc. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substituents as described herein for alkyl. Non-limiting unsubstituted alkynyl groups include C 2-8 alkynyl, C 2-6 alkynyl, C 2-5 alkynyl, C 2-4 alkynyl, or C 2-3 alkynyl. Exemplary non-limiting alkynyl groups include ethynyl (-C≡CH), 1-propynyl (-C≡CCH3), 2-propynyl or propargyl (-CH2C≡CH), 1-butynyl (-C≡CCH2CH3), 2-butynyl (-CH2C≡CCH3), 3-butynyl (-CH2CH2C≡CH), etc.

[0167] "Alkynylene" means the polyvalent (e.g., divalent) form of an alkynyl group, which is an optionally substituted C 2-24It is an alkyl group. The alkynylene group can be cyclic or acyclic. The alkynylene group can be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more substituents as described for alkyl in this specification. Exemplary non-limiting alkynylene groups include -C≡C- or -C≡CCH2-.

[0168] What "amide" means is -N(R N1 )C(O)-, where R N1 is H, optionally substituted alkyl, or optionally substituted aryl.

[0169] What "amino" means is -NR N1 R N2 , where R N1 and R N2 are each independently H, optionally substituted alkyl, or optionally substituted aryl, or R N1 and R N2 together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein.

[0170] What "aminoalkyl" means is an alkyl group as defined herein substituted with an amino group as defined herein.

[0171] What "aminoaryl" means is an aryl group as defined herein substituted with an amino group as defined herein.

[0172] What "aryl" means is a group containing a carbon-based aromatic group including, but not limited to, phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, etc. For example, condensed benzo-C such as indanyl, tetrahydronaphthyl, fluorenyl, etc.4-8 It includes a cycloalkyl radical (e.g., as defined herein). The term aryl includes heteroaryl, which is defined as a group containing an aromatic group in which at least one heteroatom is incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl is also included in the term aryl and defines a group containing an aromatic group that does not contain a heteroatom. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one, two, three, four, or five substituents, such as any of those described herein for alkyl.

[0173] "Azido" means -N3.

[0174] "Branched alkenyl" means an isomer of a straight-chain alkenyl compound and has an alkyl group bonded to the main carbon chain.

[0175] "Cyano" means -CN.

[0176] "Carbonyl" means a -C(O)- group, which can also be represented as >C=O.

[0177] "Cycloalkyl" means, unless otherwise specified, a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group having 3 to 8 carbon atoms. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.]heptyl, etc. The cycloalkyl group can also be substituted or unsubstituted. For example, the cycloalkyl group can be substituted with one or more groups as described herein for alkyl.

[0178] "Deposition" or "vapor deposition" means a process of forming a metal layer on one or more surfaces of a substrate from a vaporized precursor composition(s) containing one or more metal-containing compounds. The metal-containing compounds are vaporized and directed to and / or contacted with one or more surfaces of a substrate (i.e., a semiconductor substrate or semiconductor assembly) placed in a deposition chamber. Typically, the substrate is heated. These metal-containing compounds form a non-volatile, thin, and uniform metal-containing layer on the surface(s) of the substrate. One operation of this method is one cycle, and this process can be repeated for the number of cycles necessary to obtain the desired metal thickness.

[0179] "Dicarbonyl" means any moiety or compound containing two carbonyl groups, as defined herein. Non-limiting examples of dicarbonyl moieties include 1,2-dicarbonyl (e.g., R C1 -C(O)-C(O)R C2 wherein R C1 and R C2 are each independently optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or leaving group), 1,3-dicarbonyl (e.g., R C1 -C(O)-C(R 1a R 2a )-C(O)R C2 wherein R C1 and R C2 are each independently optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or leaving group, and R 1a and R 2a are each independently H, or an optional substitution component provided for alkyl as defined herein), and 1,4-dicarbonyl (e.g., R C1 -C(O)-C(R 1a R 2a )-C(R 3a R 4a )-C(O)R C2 wherein R C1 and R C2is independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group, R 1a , R 2a , R 3a , and R 4a is independently H, or an optional substitution component provided for alkyl as defined herein).

[0180] "Halo" means F, Cl, Br, or I.

[0181] "Halo-containing substitution component" means a group containing halo, such as a haloaliphatic group or a haloalkyl group.

[0182] "Haloaliphatic" means an aliphatic group as defined herein substituted with one or more halos.

[0183] "Haloalkenyl" means an alkenyl group as defined herein substituted with one or more halos.

[0184] "Haloalkynyl" means an alkynyl group as defined herein substituted with one or more halos.

[0185] "Haloalkyl" means an alkyl group as defined herein substituted with one or more halogens. Non-limiting unsubstituted haloalkyl groups include C 1-2 haloalkyl, C 1-3 haloalkyl, C 1-4 haloalkyl, C 1-5 haloalkyl, C 1-6 haloalkyl, C 2-3 haloalkyl, C 2-4 haloalkyl, C 2-5 haloalkyl, C 2-6 haloalkyl, or C 3-6 haloalkyl. Other non-limiting haloalkyl groups include -CX y H3-y (where y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I)); -CX z H 2-z CX y H 3-y (where z is 0, 1, or 2, y is 0, 1, 2, or 3, each X is independently halo (F, Cl, Br, or I), and at least one of z or y is not 0); -CH2CX y H 3-y (where y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I)); -CX z1 H 2-z1 CX z2 H 2-z2 CX y H 3-y (where z1 and z2 are each independently 0, 1, or 2, y is 0, 1, 2, or 3, each X is independently halo (F, Cl, Br, or I), and at least one of z1, z2, or y is not 0); and -CX z H 1-z [CX y1 H 3-y1 [CX y2 H 3-y2 (where z is 0 or 1, y1 and y2 are each independently 0, 1, 2, or 3, each X is independently halo (F, Cl, Br, or I), and at least one of z, y1, or y2 is not 0).

[0186] "Haloalkylene" means an alkylene group as defined herein substituted with one or more halos.

[0187] "Heterocyclyl", unless otherwise specified, means a three-membered, four-membered, five-membered, six-membered, or seven-membered ring containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halogen). The three-membered ring has zero to 1 double bond, the four-membered and five-membered rings have zero to 2 double bonds, and the six-membered and seven-membered rings have zero 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 an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocycle (e.g., indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, etc.). Examples of heterocycles include acridinyl, adenyl, alloxazinyl, azadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azononyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyrronyl, benzquinolinyl, benzquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiadinonyl, benzothiadinyl, benzothiopyranyl, benzothiopyrronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl,Benzoxathionyl, benzoxazepinyl, benzoxazinyl, benzoxazothionyl, benzoxazolnonyl, benzoxazolinyl, benzoxazolyl, benzylsulfamyl, benzylsulfthymyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzoisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzooxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydropyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxolanyl, dioxenyl, dioxinyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guanylinyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazolyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidinyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthyridinyl, naphthopyranonyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl,Naphthoxindolyl, naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanonyl, oxetanyl, oxetyl, octenail, oxyindolyl, oxiranyl, oxobenzisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolidizinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrilium, quinazolinyl, quinolinyl, quinolidinyl (e.g., 4H-quinolidinyl), quinoxalinyl, quinuclidinyl, selenadiazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiadiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthylenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thietyl, thiaranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinylThiophenyl, thiopyranyl, thiopyrionyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, urethidinyl, urethinyl, uracil, uridinyl, xanthenyl, xanthinyl, xanthionyl, etc., and their modified forms (e.g., including one or more oxo and / or amino) and their salts. The heterocyclyl group can be substituted or unsubstituted. For example, the heterocyclyl group can be substituted with one or more substituents as described herein for aryl.,

[0188] What “hydroxyl” means is -OH.

[0189] What “imino” means is -NR-, and R can be H or optionally substituted alkyl.

[0190] What “isocyanato” means is -NCO.

[0191] What “isothiocyanato” means is -N=C=S.

[0192] What “oxo” means is =O group.

[0193] What “oxy” means is -O-.

[0194] What “silyl” means is -SiR 1 R 2 R 3 group or -SiR 1 R 2 - group. In some embodiments, R 1 、R 2 、and R 3 are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In certain embodiments, R 1 、R2 and R 3 each independently is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyl group is -Si(R) a (OR) b (NR2) c wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and a, b, and c are each ≧0 and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0195] "Silyloxy" means -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, the silyloxy group is -O-SiR 1 R 2 R 3 wherein R 1 , R 2 , and R 3 each independently is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In certain embodiments, R 1 , R 2 and R 3 each independently is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyloxy group is -O-Si(R) a (OR)b (NR2) c wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and a, b, and c are each ≧0 and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0196] When each of the above terms is used, it is meant to include both substituted and unsubstituted sites. Substitution may be by one or more groups such as alcohol, ether, ester, amide, sulfone, sulfide, hydroxyl, nitro, cyano, carboxy, amine, heteroatom, lower alkyl, lower alkoxy, lower alkoxycarbonyl, alkoxyalkoxy, acyloxy, halogen, trifluoromethoxy, trifluoromethyl, alkyl, aralkyl, alkenyl, alkynyl, aryl, cyano, carboxy, carboalkoxy, carboxyalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, oxo, arylsulfonyl, and aralkylaminocarbonyl, or any of the substitution components of the preceding paragraph, or any of these substitution components linked directly or by a suitable linker. The linker is typically a short chain of 1 to 3 atoms including any combination of -C-, -C(O)-, -NH-, -S-, -S(O)-, -O-, -C(O)- or -S(O)O-. The ring may be substituted multiple times.

[0197] The term "lower" when modifying "alkyl", "alkenyl", "alkynyl", "alkoxy", or "alkoxycarbonyl" refers to C1-C6 units of a particular functionality. For example, "lower alkyl" means C1-C6 alkyl.

[0198] "Substituted" means having one or more substitution sites that, in their presence, do not prevent the desired function or reactivity. Examples of substitution components include alkyl, alkenyl, alkynyl, cycloalkyl (non-aromatic ring), Si(alkyl)3, Si(alkoxy)3, alkoxy, amino, alkylamino, alkenylamino, amide, amidine, guanidine, hydroxyl, thioether, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphoric ester, phosphonic acid, cyano, halo, acylamino, imino, sulfhydryl, alkylthio, thiocarboxylate, dithiocarboxylate, sulfate, sulfato, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azide, heterocyclyl, ether, ester, silicon-containing site, thioester, or combinations thereof. The substitution components may themselves be substituted. For example, an amino substitution component may itself be mono-substituted or independently di-substituted by further substitution components as defined above such as alkyl, alkenyl, alkynyl, and cycloalkyl (non-aromatic ring).

[0199] "Thiocyanato" means -SCN.

[0200] "Unsubstituted" means that the vacant valence of an atom is occupied by hydrogen. Also, when nothing is specified as occupying the vacant valence position of an atom, it is hydrogen.

[0201] As used herein, the term "about" is understood to account for a minor increase and / or decrease above and below the recited value, provided that these changes do not significantly affect the desired function of the parameter beyond the recited value(s). In some cases, "about" encompasses ±10% of the recited value. As used herein, this term modifies any recited value, range of values, or endpoints of one or more ranges.

[0202] In this specification, terms such as "upper", "bottom", "upper part", "lower part", "above", and "below" are used to establish relative relationships between structures. The use of these terms does not indicate or require that a particular structure must be in a particular position within the device.

[0203] In the embodiments disclosed below, the deposition of materials onto substrates such as wafers, substrates, or other workpieces will be described. The workpiece may have various shapes, sizes, and materials. In this application, the terms "semiconductor wafer", "wafer", "substrate", "wafer substrate", and "partially manufactured integrated circuit" are used interchangeably. One of ordinary skill in the art will understand that the term "partially manufactured integrated circuit" may refer to a silicon wafer that is at any of many stages of integrated circuit fabrication thereon. Wafers or substrates used in the semiconductor device industry typically have diameters of 200 mm, 300 mm, or 450 mm. Unless otherwise specified, the process details (e.g., flow rates, power levels, etc.) listed in this specification relate to the processing of a 300 mm diameter substrate or a chamber configured to handle a 300 mm diameter substrate, but can be appropriately scaled for other substrate sizes or chambers. In addition to semiconductor wafers, various articles such as printed circuit boards can be used as other workpieces for which the embodiments disclosed herein can be used. This process and apparatus can be used in the manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, and the like.

[0204] "Tin oxide" as used herein refers to Sn x O y and is referred to as including all possible stoichiometric possibilities, including integer and non-integer values of x and y. For example, "tin oxide" includes compounds having the formula SnO n (where 1 < n < 2 and n can be an integer or non-integer value). "Tin oxide" includes SnO 1.8Stoichiometric compounds such as can also be included. "Tin oxide" includes tin dioxide (SnO2 or stannic oxide) and tin monoxide (SnO or stannous oxide). "Tin oxide" includes natural and synthetic variations and all possible crystal structures and molecular structures. "Tin oxide" includes amorphous tin oxide.

[0205] "Unsaturated" means a site containing a double or triple carbon-carbon bond.

[0206] "Unsaturated substitution component" means a double bond or triple bond containing an aliphatic chain, cyclic group, aryl group, or heteroaryl group.

[0207] Other features and advantages of the present invention will become apparent from the following description and claims.

Brief Description of the Drawings

[0208]

Figure 1

[0209]

Figure 2

[0210]

Figure 3A

[0211]

Figure 3B

[0212]

Figure 4A

[0213]

Figure 4B

[0214]

Figure 4C

[0215]

Figure 5A

[0216]

Figure 5B

[0217]

Figure 6

[0218]

Figure 7

[0219]

Figure 8

[0220]

Figure 9

[0221]

Figure 10

[0222]

Figure 11

[0223]

Figure 12

DETAILED DESCRIPTION OF THE INVENTION

[0224] The present disclosure relates to a precursor composition for forming an irradiation-sensitive film. In particular, the present disclosure is directed to a metal-containing precursor having a haloaliphatic substitution component or an unsaturated substitution component, or other reactive sites, which advantageously reacts in the presence of extreme ultraviolet exposure to form a resist film with improved etching resistance and / or reduced shrinkage during processing. Alternatively, a metal-containing precursor having a haloaliphatic substitution component or an unsaturated substitution component, or other reactive sites, may be used to pattern a structure having a carbon-containing underlying layer, thereby advantageously reacting with the underlying layer to enhance the adhesion between the resist film and the underlying layer.

[0225] In this specification, specific embodiments of the present disclosure are referred to in detail. Examples of specific embodiments are shown in the accompanying drawings. While the present disclosure is described in conjunction with these specific embodiments, it will be understood that the present disclosure is not intended to be limited to those specific embodiments. Rather, the intention is to cover alternatives, modifications, equivalents that may be included within the spirit and scope of the present disclosure. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. The present disclosure may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the present disclosure.

[0226] EUV lithography uses a patterned EUV resist to form a mask for use in etching the underlying layer. The EUV resist may be a polymer-based chemically amplified resist (CAR) produced by liquid-based spin-on technology or dry vapor deposition. Alternatives to CAR are available from, for example, Inpria (Corvallis, Oregon), and are, for example, directly photopatternable metal oxide-containing films as described in U.S. Patent Publication Nos. US2017 / 0102612, US2016 / 0216606, and US2016 / 0116839, the disclosures of at least those directly photopatternable metal oxide-containing films being incorporated herein by reference. Such films may be produced by spin-on technology or dry vapor deposition. The metal oxide-containing film is directly (i.e., without using a separate photoresist) patternable by EUV exposure in a vacuum environment that provides a patterning resolution of less than 30 nm, as described, for example, in U.S. Patent No. 9,996,004, issued June 12, 2018, entitled "EUV PHOTOPATTERNING OF VAPOR-DEPOSITED METAL OXIDE-CONTAINING HARDMASKS" and / or International Application PCT / US19 / 31618, filed May 9, 2019, published as International Publication WO2019 / 217749, entitled "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS", the disclosures of at least those regarding the composition, deposition, and patterning of the directly photopatternable metal oxide film for forming such EUV resist masks being incorporated herein by reference. Typically, patterning includes exposing the EUV resist with EUV radiation to form a photopattern in the resist and then developing to remove a portion of the resist according to the photopattern to form the hard mask.

[0227] Directly photo-patternable EUV or DUV resists can be composed of, or can include, metals and / or metal oxides mixed in an organic component. The metal / metal oxide is highly promising in that it can enhance the adsorption of EUV or DUV photons, generate secondary electrons, and / or increase the etching selectivity with respect to the underlying film stack and device layer. Heretofore, these resists have been developed using a wet (solvent) approach, which requires moving the wafer to a track, exposing it there to a developing solvent, drying it, and then baking it. The wet development step not only limits productivity but also may cause line collapse due to surface tension effects when the solvent evaporates between fine features.

[0228] Typically, a resist can be employed as a positive-tone resist or a negative-tone resist by controlling the chemical properties of the resist and / or the solubility or reactivity of the developer. It is beneficial to have an EUV or DUV resist that functions as a negative-tone resist or a positive-tone resist.

[0229] Resist Film and Method Thereof The present disclosure relates to an organometallic resist film and a method thereof. In certain embodiments, the film comprises a halogen-containing organometallic material. Such materials can provide compact or high-density films, which as a result improve the radiation absorption rate and limit shrinkage induced by baking and shrinkage induced by radiation. High-density films are achievable by employing precursors having relatively small radiation-cleavable groups. Such groups can be, for example, C 1-2 (halo)aliphatic groups. Compared to the cleavage of larger groups (e.g., C 3-12 aliphatic groups), the smaller C 1-2The cleavage and release of the (halo)aliphatic group will form smaller voids (where the group used to be) upon exposure. Such voids can contribute to film shrinkage when the exposed film is further processed (e.g., post-exposure, post-exposure etching, or other processes). By minimizing the size of the voids, film shrinkage can be minimized.

[0230] Film shrinkage can contribute to various undesirable effects. For example, if the exposed area shrinks dramatically, the dose-to-size (DtS) becomes high, and the application of such a resist as an etching hard mask may be limited. Thus, the films herein can be employed to avoid film shrinkage. Such films can, for example, lower the DtS after subsequent development and / or use as an etching hard mask.

[0231] Also, radiation absorption can be improved. For example, the smaller the size of the radiation-cleavable group, the higher the density of the film that can be obtained, thereby providing additional atoms for radiation absorption (e.g., per 1 cm -2 hit). Further, halogen atoms have a higher EUV absorption rate compared to hydrogen atoms. Thus, the presence of a halogen substitution component on the radiation-cleavable group can provide EUV photosensitive sites with increased absorption rates. In other embodiments, the haloaliphatic group or a halo atom from such a group is incorporated into a film where the EUV absorption rate of the halogen is higher than that of hydrogen. Such groups (e.g., haloaliphatic groups or halo atoms) can be provided by bonding to a metal atom to bridge two metal atoms or to a ligand. The higher-absorbing film can, for example, reduce line width roughness (LWR) after subsequent development without requiring a higher dose, and can provide a thinner film not limited to a minimum thickness, resulting in sufficient absorption and effective pattern formation. Such thin films can be processed using optical applications with a shallow depth of focus.

[0232] The metal-containing precursor can be used alone or together with additional precursors such as ligand-containing precursors in order to further modify the functional groups bonded to M in the metal-containing precursor. The ligand-containing precursor can react with the metal-containing precursor to further install L groups and / or R groups on M.

[0233] By combining such a metal-containing precursor with a ligand-containing precursor, a further metal-containing precursor can be provided. Thus, the final combination of the cleavable group (R) and / or ligand (L) can be changed in situ (in the chamber) or prior to sending it to the chamber for deposition.

[0234] Examples of the ligand-containing precursor include an organolithium compound (e.g., LiL), an organosodium compound (e.g., NaL), an organomagnesium compound (e.g., MgL2), a Grignard reagent (e.g., MgLX where X is a halo), an organozinc compound (e.g., ZnL2), or an organoaluminum compound (e.g., AlL3). In certain embodiments, such reagents are not employed in the deposition chamber but are employed for synthesizing the precursor prior to sending it to the deposition chamber.

[0235] Examples of useful ligands in the ligand-containing precursor include organic moieties (e.g., optionally substituted alkyl, optionally substituted amino, optionally substituted alkoxy, optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiMe3)2), optionally substituted trialkylsilyl, or others), any of those described herein. Other ligand-containing precursors include aliphatic halides (e.g., RX where X is a halo and R is optionally substituted alkyl) or haloaliphatic halides (e.g., RX where X is a halo and R is optionally substituted haloalkyl). Non-limiting R groups include optionally substituted C 1-2 haloalkyl, e.g., -CX z H 3-z or -CH2CX z H3-z (where z is 1, 2, or 3), and optionally substituted C 1-4 alkyl, such as -C n H 2n+1 (where n is 1 or 2), or -C n H 2n-1 or -C n H 2n-3 (where n is 2, 3, or 4).

[0236] The present disclosure also generally includes any useful method that employs a metal-containing precursor having an optional ligand-containing precursor as described herein. Such methods can include any useful lithography process, deposition process, radiation exposure process, development process, and post-application process as described herein. In the following, techniques related to EUV processes will be described, but such techniques may be applied to other next-generation lithography techniques. Various radiation sources can be employed, such as EUV (usually about 13.5 nm), DUV (deep UV, usually in the range of 248 nm or 193 nm using an excimer laser source), X-rays (including EUV in the low-energy range of the X-ray range), and electron beams (including a wide energy range).

[0237] Exemplary methods can include, in addition to sending the metal-containing precursor(s) to a substrate, simultaneously or sequentially sending the metal-containing precursor(s) and the ligand-containing precursor(s) to the substrate. For example, in FIG. 1, a non-limiting process 100 is provided that includes depositing the metal-containing precursor 30 and an optional ligand-containing precursor 32 onto a substrate 111 at 101. Such co-deposition can provide a high-density film 112 having a matrix of metal atoms and (halo)aliphatic components or aliphatics. Such deposition can include dry deposition.

[0238] When using a ligand-containing precursor, the delivery of the metal-containing precursor and the ligand-containing precursor can be carried out in any useful order. When delivering them continuously, optional operations can include purging the chamber to remove unreacted precursors. Such purging can also include using an inert gas to remove metal-containing precursors or ligand-containing precursors that are present in vapor form and thus do not deposit on the substrate.

[0239] Such films can be deposited by any useful method described herein. Exemplary deposition techniques include chemical vapor deposition (CVD), plasma-enhanced CVD (PE-CVD), low-pressure CVD (LP-CVD), atomic layer deposition (ALD) (e.g., thermal ALD and plasma-enhanced ALD (PE-ALD)), molecular layer deposition (MLD), spin-coat deposition, physical vapor deposition (PVD) (including PVD co-sputtering), sputter deposition, electron beam (e-beam) deposition (including e-beam co-deposition), etc., or combinations thereof. Other deposition processes and conditions are described herein.

[0240] The metal-containing precursor and / or ligand-containing precursor can optionally be deposited in the presence of one or more counterreactants. The counterreactant preferably has the ability to replace a reactive site, ligand, or ion (e.g., L in the various formulas herein) such that at least two metal atoms are linked via a chemical bond. Exemplary counterreactants include oxygen-containing counterreactants such as O2, O3, water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, dihydroxyalcohols or polyhydroxyalcohols, acetamide, fluorinated dihydroxyalcohols or fluorinated polyhydroxyalcohols, fluorinated glycols, formic acid, and other sources of hydroxyl sites, and combinations thereof. In various embodiments, the counterreactant reacts with the metal-containing precursor and / or ligand-containing precursor by forming an oxygen bridge between adjacent metal atoms. Other potential counterreactants include hydrogen sulfide and hydrogen disulfide which can bridge metal atoms via sulfur bridges, and bis(trimethylsilyl)tellurium which can bridge metal atoms via tellurium bridges. Further, hydrogen iodide may be utilized to incorporate iodine into the film. Still other counterreactants can include the chalcogenide-containing precursors or chalcogenide-containing compounds described herein.

[0241] Various process conditions for deposition can be varied and optimized. For example, the deposition (e.g., of the metal-containing precursor and / or ligand-containing precursor) can be carried out at a temperature of about 20 - 400 °C (e.g., about 50 - 300 °C, about 100 - 200 °C, or about 150 °C). In some embodiments, the metal-containing precursor(s) and / or ligand-containing precursor(s) have a thermal decomposition point higher than the process temperature so as to result in a self-limiting surface reaction. Non-limiting pressure conditions include the range of about 0.1 - 50 Torr, such as about 1 - 15 Torr. In some embodiments, the metal-containing precursor(s) and / or ligand-containing precursor(s) have a vapor pressure greater than 0.5 Torr at 100 °C or less.

[0242] The process step times for each operation can include the following ranges: administration of the metal-containing precursor for about 0.1 to 10 seconds, administration of the ligand-containing precursor for about 0.1 to 60 seconds, and a purge period for about 0.1 to 60 seconds.

[0243] Deposition can be repeated for any number of cycles. Each cycle can include a deposition operation, which can include deposition of the metal-containing precursor, co-deposition of the metal-containing precursor and the ligand-containing precursor, or sequential deposition of the metal-containing precursor and the ligand-containing precursor and an optional purge operation. Such cycles can be repeated for any useful number of cycles, for example, 1 to 1000 cycles, to deposit to a desired film thickness.

[0244] When deposited to the desired film thickness, a post-deposition treatment step may be performed. In one example, such post-deposition treatment involves exposing the film to a long-term administration (or soak) using a soak precursor. The soak can be used to increase the EUV absorbance of the film. In one embodiment, the soak precursor is a metal-containing precursor, and using this soak precursor increases the concentration of metal atoms in the film. In other embodiments, the soak precursor is a ligand-containing precursor. The soak precursor can be the same as or different from the metal-containing precursor used in the deposition process. The soak may be performed under conditions similar to the deposition process, but typically the administration time may be relatively long, for example, in the range of 30 seconds to 30 minutes.

[0245] The methods herein can include depositing directly onto a substrate or onto a layer disposed on the surface of the substrate. In one example, the substrate can include an adhesion layer or an underlayer, which can be an organic underlayer or an intermediate etch layer.

[0246] The resist film can have any useful structure. In one embodiment, the film has a thickness of about 0.5 nm to about 100 nm (for example, about 5 nm to about 100 nm, and other thicknesses described herein). The film can include an optional underlayer or an optional surface activation step prior to deposition of the metal-containing precursor.

[0247] The film can have a vertical gradient characterized by a vertical change in EUV absorbance. In some examples, an increase in EUV absorbance along a depth (e.g., from the top surface of the film towards the substrate) can correspond to an increase in metal content or halogen content along the same depth through the film layer. Non-limiting gradients include linear gradients, exponential gradients, sigmoid gradients, etc. In certain embodiments, a gradient density film of EUV-sensitive sites can create more homogeneous film properties across the EUV exposure area at all depths within the film, thereby improving the development process, improving EUV sensitivity, and / or improving patterning quality (e.g., improving line width roughness (LWR) and / or improving line edge roughness (LER), etc.).

[0248] The resist film can include an organometallic material, e.g., an organometallic oxide (e.g., RM(MO) n where M is a metal and R is a halogenated organic moiety having one or more carbon atoms and one or more halogen atoms). The substrate can include any useful wafer, feature(s), layer(s), or device(s). In some embodiments, the substrate is a silicon wafer having any useful feature (e.g., an irregular surface topography), layer (e.g., a photoresist layer), or device.

[0249] The radiation-sensitive film can include metal components and organic substitution components, each of which may include UV-sensitive sites, DUV-sensitive sites, or EUV-sensitive sites. Non-limiting examples of these include, for example, 1×10 7 cm 2Metals, metalloids, or atoms having a high EUV absorption cross-section of 1 / mol or more can be mentioned. In other embodiments, the component contains M or is M (for example, M can be tin (Sn), bismuth (Bi), tellurium (Te), cesium (Cs), antimony (Sb), indium (In), molybdenum (Mo), hafnium (Hf), iodine (I), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), platinum (Pt), lead (Pb), Xe, or a combination thereof). In some embodiments, the component contains a metal-containing precursor, a ligand-containing precursor, or a reaction product thereof.

[0250] The film can be homogeneous. In certain embodiments, the homogenized matrix can be an alloy film. Co-deposition can be caused in any useful method (e.g., CVD) that uses the co-flow of both a metal-containing precursor and a ligand-containing precursor.

[0251] The obtained film can be used as a photoresist. In certain non-limiting embodiments, the layer can contain sites that promote radiation absorption after radiation exposure (e.g., exposure to UV, DUV, and / or EUV radiation). In further embodiments, the organometallic layer can contain metal centers and halogen atoms that promote radiation absorption. After deposition, the film can be patterned by radiation exposure and then developed, thereby providing a negative tone resist or a positive tone resist. Such a method can include any useful lithography process, deposition process, EUV exposure process, development process, and post-application process described herein. In certain embodiments, the film exhibits minimal film shrinkage after EUV exposure, development, and / or post-application processes.

[0252] Returning to FIG. 1, further steps can include providing an exposed film having an EUV exposure range 112b and an unexposed EUV range 112c by patterning the film by EUV exposure 102. Patterning can include the use of a mask 114 having EUV transparent regions and EUV opaque regions, and the EUV beam 115 passes through the EUV transparent regions and is incident on the film 112. EUV exposure can include, for example, an exposure having a wavelength in the range of about 10 nm to about 20 nm (e.g., about 13.5 nm) in a vacuum environment.

[0253] Method 100 can further include developing the film 103, thereby (i) removing the EUV exposure range to provide a pattern in a positive tone resist film, or (ii) removing the unexposed EUV range to provide a pattern in a negative tone resist. The path (i) of FIG. 1 results in selectively removing the EUV exposure range 112b. Alternatively, the path (ii) of FIG. 1 results in maintaining the EUV exposure region 112b after development.

[0254] The developing step can include the use of a halide chemical in the gas phase (e.g., an HBr chemical), or the use of an aqueous or organic solvent (e.g., as described herein) in the liquid phase. The developing step can include any useful experimental conditions. For example, low pressure conditions (e.g., about 1 to 100 mTorr), plasma exposure (e.g., in the presence of a vacuum), and / or thermal conditions (e.g., about -10 to 100 °C) that may be combined with any useful chemical (e.g., a halide chemical or an aqueous chemical). Developing can include, for example, halide-based etchants such as HCl, HBr, H2, Cl2, Br2, BCl3, or combinations thereof, and any halide-based developing process described herein, an aqueous alkaline developer, or an organic developer. Further developing process conditions are described herein.

[0255] Optional steps may be performed to further adjust, modify, or process the EUV-sensitive film(s), substrate, photoresist layer(s), and / or any method herein. FIG. 2 provides a flowchart of an exemplary method 200 having various operations including optional operations. As shown, in operation 204, a resist film (e.g., in a chamber) can be provided by providing a metal-containing precursor and an optional ligand-containing precursor in the optional presence of a counter-reagent.

[0256] In one example, the method can include an optional step 206 of cleaning the back surface or bevel of the substrate or removing edge beads of the photoresist deposited in a previous step. Such a cleaning or removal step may be useful for removing particles that may be present after depositing the film layer. The removal step can include treating the wafer using a wet metal oxide (MeOx) edge bead removal (EBR) step.

[0257] In another example, the method can include an optional step 208 of performing a post-application bake (PAB) on the deposited photoresist layer, thereby removing residual moisture from the layer to form a film or pretreating the photoresist layer in any useful manner. The optional PAB can be performed after film deposition and before EUV exposure, and the PAB can increase the EUV sensitivity of the film by including a combination of heat treatment, chemical exposure, and moisture, thereby reducing the EUV dose and developing a pattern in the film. In certain embodiments, the PAB step is performed at a temperature above about 100°C, or at a temperature of about 100 - 200°C or 100 - 250°C. In some examples, the PAB is not performed within the method.

[0258] In operation 210, the film is exposed to EUV radiation to develop a pattern. Typically, EUV exposure changes the chemical composition of the film, creating a contrast in etch selectivity that can be used to remove a portion of the film. Such contrast can provide a positive-tone resist or a negative-tone resist as described herein.

[0259] In yet another example, the method can include an optional step 212 of performing a post-exposure bake (PEB) of the exposed film to further remove residual moisture, or to promote chemical condensation within the film, or to post-process the film in any useful way. In another example, the method can include curing the patterned film (e.g., after development), thereby providing a resist mask disposed on the upper surface of the substrate. The curing step can include any useful process for further cross-linking or reacting the non-EUV-exposed or exposed regions, such as exposing to a plasma (e.g., O2, Ar, He, or CO2 plasma), exposing to ultraviolet radiation, annealing (e.g., at a temperature of about 180 - 240 °C), thermal baking, or combinations thereof that may be useful for a post-development bake (PDB) step. Additional post-application processes are described herein and may be performed as optional steps of any of the methods described herein.

[0260] Next, in operation 214, a photoresist (PR) pattern is developed. In various embodiments of development, the exposed regions are removed (positive tone) or the unexposed regions are removed (negative tone). In various embodiments, these steps may be dry processes and / or wet processes.

[0261] In some embodiments, the process includes all dry processes, such as dry deposition of a film (e.g., using a precursor in vapor form and a counter-reactant including water vapor) and dry development of an exposed film. Without wishing to be bound by theory, such a film can provide a negative tone resist, in which the radiation-exposed regions provide a non-volatile material and the radiation-unexposed regions provide volatile by-products when exposed to a dry development chemical reaction (e.g., any of the vapor-based etching chemical reactions described herein). In this way, a vapor-phase etchant can be used to react with the unexposed film to provide volatile by-products, and the volatile chemicals can be removed even in their vapor form.

[0262] In other embodiments, wet processes can be employed in one or more operations. Such processes can include, in addition to dry deposition of a film (e.g., using a precursor in vapor form and a counter-reactant including water vapor) and wet development of an exposed film (e.g., using any of the wet developers described herein), wet deposition of a film (e.g., using a precursor in a solvent) and dry development of an exposed film, and wet deposition of a film and wet development of an exposed film. Without wishing to be bound by theory, such a film can provide a positive tone resist, in which the radiation-exposed regions provide a material that can be dissolved in a solvent (e.g., including a metal halide bond such as tin halide), and the radiation regions provide a material that is more resistant to solvent dissolution.

[0263] During the deposition step, patterning step, and / or development step, any useful kind of chemical reaction can be employed. Such steps may be based on a dry process that employs a chemical reaction in the gas phase or a wet process that uses a chemical reaction in the wet phase. Various embodiments include combinations of all dry operations such as film formation by vapor deposition, (EUV) lithography photopatterning, dry stripping, and dry development. Various other embodiments include those that advantageously combine the dry processing operations described herein with wet processing operations, for example, a spin-on EUV photoresist (wet process) such as those available from Inpria may be combined with dry development or other wet or dry processes described herein. In various embodiments, wafer cleaning may be a wet process as described herein and other processes may be dry processes. In yet other embodiments, a wet development process may be used.

[0264] While not limiting the mechanism, function, or utility of the present technology, the dry process of the present technology can provide various benefits as compared to wet development processes known in the art. For example, using the dry vapor deposition methods described herein, a thinner and less defective film can be deposited than can be achieved using a spin coating method, where the exact thickness of the deposited film can be adjusted and controlled by simply increasing or decreasing the length of the deposition step or sequence. Thus, the dry process may allow for greater adjustability and provide further critical dimension (CD) control and scum removal. Dry development can improve performance (e.g., prevent line collapse due to surface tension in wet development) and / or throughput (e.g., by eliminating wet development tracks). Other advantages may include the elimination of the need for organic solvent developers, reduced sensitivity to adhesion problems, elimination of the need for the application and removal of wet resist formulations (e.g., eliminating scum and pattern distortion), improved line edge roughness, the ability to pattern directly on the topography of the device, the ability to tailor hard mask chemistry to specific substrate and semiconductor device designs, and the elimination of other solubility-based limitations. Further details, materials, processes, steps, and apparatus are described herein.

[0265] Descum / Smoothing / Hardening In some cases, there may be scum (a material in the open area of unexposed areas, such as in the area of EUV resist after development, often having a high metal concentration like a cluster) or roughness (having the same composition but on the sidewalls of etched features within the developed pattern). These can be removed in a descum / smoothing operation by a He (or other inert gas) plasma desorption operation. Suitable process conditions for such a dry descum / smoothing operation may be as follows: a reaction gas flow of 100 - 500 scccm (e.g., 500 sccm of He), a temperature of -10 - 120 °C (e.g., -10 °C), a pressure of 5 - 20 mT (e.g., 10 mT), a plasma power of 100 - 300 W (e.g., 300 W), a high frequency (e.g., 13.56 MHz), a wafer bias of 50 - 300 V b and a time of about 1 - 3 seconds (e.g., 2 seconds).

[0266] He deposition, descum, and cleaning of unexposed resist residues can also have the incidental benefit of enhancing the hard mask function in subsequent operations for etching the underlying substrate by hardening and solidifying the exposed resist. This resist hardening is achieved by exposing the EUV-exposed resist to UV radiation generated from the He plasma and can continue even after the descum / smoothing is completed with the bias turned off. If descum / smoothing is not necessary or not performed, He plasma hardening may be alternatively carried out.

[0267] In some embodiments, He plasma descum / smoothing may be cycled with dry development as described above to obtain better results. In this way, for example, most of the organic components in unexposed areas such as pattern regions can be removed by dry development, and then a part of the surface-concentrated metal can be removed by a short-time He plasma operation, opening access to the remaining underlying organic matter, and the organic matter can be removed in subsequent dry development operations / cycles. Use another cycle of He plasma to remove any remaining metal, resulting in a clean and smooth feature surface. This cycle can be continued until all or substantially all of the scum and rough residues are removed, resulting in a clean and smooth feature surface.

[0268] This He desorption descum and smoothing is further illustrated with reference to an organic tin oxide-based EUV photoresist dry-developed using the HBr chemistry described herein. After the first HBr development operation, SnOx residues remain on the substrate surface underlying the EUV photoresist in the unexposed regions. By desorption, the brominated SnOx surface layer of the residue can be removed, exposing the higher concentration of organic matter in the residue. Next, a second cycle of HBr dry development can further remove the residues. This cycle can be continued as needed.

[0269] U.S. Provisional Patent Application No. 63 / 203,507, filed on July 26, 2021, entitled "Multistep Post Exposure Treatment to Improve Dry Development Performance of Metal Containing Resist", U.S. Provisional Patent Application No. 62 / 705,616, filed on July 20, 2020, entitled "Integrated Dry Processes for Patterning Radiation Photoresist Patterning", U.S. Provisional Patent Application No. 63 / 364,180,507, filed on May 4, 2022, entitled "Post-Development Treatment of Metal-Containing Photoresist", and U.S. Provisional Patent Application No. 63 / 200,921, filed on April 2, 2021, entitled "Control of Metallic Contamination from Metal-Containing Photoresist" are hereby incorporated by reference in their entirety.

[0270] Metal-containing precursor The metal-containing precursor can have any useful number and type of cleavable group(s) and / or ligand(s). Cleavable groups (L) can be characterized by their ability to react in the presence of patterning radiation, and ligands can be characterized by their ability to react in the presence of a counter-reagent. For example, the metal-containing precursor can include a cleavable group that desorbs in the presence of patterning radiation. Such groups can include C 1-4 (halo)aliphatic groups. In another example, the metal-containing precursor can include a ligand (e.g., a dialkylamino group or an alkoxy group) that reacts with a counter-reagent, and the ligand can introduce a linkage (e.g., an -O-linkage) between metal centers.

[0271] The metal-containing precursor can be, for example, an organometallic agent, a metal halide, or a capping agent (e.g., those described herein).

[0272] In some embodiments, the metal is characterized by a high patterning radiation absorption cross-section (e.g., an EUV absorption cross-section of 1×10 7 cm 2 / mol or greater).

[0273] In some embodiments, the metal-containing precursor has at least one optionally substituted haloalkyl group. Non-limiting haloaliphatic groups include -CX y H 3-y (where y is 1, 2, or 3 and each X is independently halo (F, Cl, Br, or I)); -CX z H 2-z CX y H 3-y (where z is 0, 1, or 2, y is 0, 1, 2, or 3, each X is independently halo (F, Cl, Br, or I), and at least one of z or y is not 0); or -CH2CX y H 3-y(y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I)). Further non-limiting haloalkyl groups include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (-CH2Cl), dichloromethyl (-CHCl2), trichloromethyl (-CCl3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (-CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoroethyl (-CHFBr), chlorofluoroethyl (-CHFCl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CH2CH2F), 2-chloroethyl (-CH2CH2Cl), 2-bromoethyl (-CH2CH2Br), 2-iodoethyl (-CH2CH2I), 2,2-difluoroethyl (-CH2CHF2), 2,2-dichloroethyl (-CH2CHCl2), 2,2-dibromoethyl (-CH2CHBr2), 2,2-diiodoethyl (-CH2CHI2), 2,2-fluoroiodoethyl (-CH2CHFI), etc. In certain embodiments, C 1-2 haloalkyl includes β-halo substituted ethyl. Further haloaliphatic groups include C 1-4 haloalkyl, C 2-4 haloalkenyl, and C 2-4 haloalkynyl.

[0274] In other embodiments, the metal-containing precursor has at least one optionally substituted alkyl group, optionally substituted alkenyl, or optionally substituted alkynyl. Non-limiting groups include -C n H 2n+1 (n is 1 or 2), -C n H 2n-1 (n is 2, 3, or 4), or -C n H 2n-3(n is 2, 3, or 4). Further non-limiting groups include methyl (-CH3), ethyl (-CH2CH3), vinyl or ethenyl (-CH=CH2), 1-propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (e.g., -CH2CH2CH=CH2), ethynyl (-C≡CH), 1-propynyl (-C≡CCH3), 2-propynyl or propargyl (-CH2C≡CH), 1-butynyl (-C≡CCH2CH3), 2-butynyl (-CH2C≡CCH3), 3-butynyl (-CH2CH2C≡CH), 2-methyl-1-propenyl (CH=C(CH3)2, isopropenyl (C(CH3)=CH2, 1-methylallyl (CH(CH3)CH=CH2), etc.

[0275] In some embodiments, the precursor has the formula M(R 1 )4 or M(R 6 )4, and when M is tin, the precursor composition contains less than about 0.5% dialiphatic metal-containing contaminants when two of the R 1 or two of the R 6 are the same aliphatic group. In some embodiments, the precursor has the formula M(R 1 )4 or M(R 6 )4, and when M is tin, the precursor composition contains less than about 0.1% dialiphatic metal-containing contaminants when two of the R 1 or two of the R 6 are the same aliphatic group.

[0276] When the desired tin-containing layer film is deposited on a plurality of wafers and stored in a FOOP, where the plurality of wafers are stored in the same container with a small gap between the wafers positioned on top of each other, it has been observed that materials can gas out from the film deposited in this way and contaminate the lower surface of the wafer above it. Since this contaminant can be transported to wafer handling devices in other areas of the manufacturing facility, a high level of contaminant is undesirable. To measure the level of gas release, the film is deposited on the wafer and housed in a FOOP, and the witness wafer above it in the slot is inverted with the clean / polished surface facing the test wafer. After several days, the witness wafer is taken out and the level of tin gas released onto the witness wafer is measured by vapor phase decomposition inductively coupled plasma mass spectrometry (VPD-ICP-MS). In the case of a film deposited from isopropyltris(dimethylamino)tin, the level of gas release may be correlated with the level of diisopropylbis(dimethylamino)tin in the precursor used. After 20 days, a film deposited from isopropyltris(dimethylamino)tin with >0.5% diisopropylbis(dimethylamino)tin showed a tin surface concentration of 1E10 atoms / cm 2 and a film deposited from isopropyltris(dimethylamino)tin with <0.1% diisopropylbis(dimethylamino)tin showed a tin surface concentration of <0.1E10 atoms / cm 2 .

[0277] In some embodiments, each ligand in the metal-containing precursor can have reactivity with a counter-reagent and / or ligand-containing precursor.

[0278] For any of the formulas herein, the metal has a high patterning radiation absorption cross-section (e.g., 1×10 7 cm 2It can be a metal having an EUV absorption cross section of / mol or more. In some embodiments, M is tin (Sn), tellurium (Te), bismuth (Bi), antimony (Sb), hafnium (Hf), or zirconium (Zr). In further embodiments, M is Sn, a is 1, and b + c is 4. In other embodiments, M is Sn, a is 1, and b + c is 2. In still other embodiments, M is Sn, a is 1, and c is 2. In certain embodiments, M is Sn(II), thereby providing a metal-containing precursor that is a Sn(II)-based compound. In other embodiments, M is Sn(IV), thereby providing a metal-containing precursor that is a Sn(IV)-based compound.

[0279] For any of the formulas herein, each L is independently H, halo, azido, cyano, alkylcarbonyl, isothiocyanato, thiocyanato, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy (e.g., -OR 1 wherein R 1 can be alkyl). In some embodiments, the optionally substituted amino is -NR 1 R 2 wherein R 1 and R 2 are each independently H or alkyl, or R 1 and R 2 together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino is -N(SiR 1 R 2 R 3 )2, and R 1 , R 2 , and R 3 are each independently alkyl. In still other embodiments, the optionally substituted trialkylsilyl is -SiR 1 R2 R 3 is, and R 1 , R 2 , and R 3 are each independently alkyl.

[0280] In other embodiments, the formula is -NR 1 R 2 a first L that is and -NR 1 R 2 a second L that is, and R 1 and R 2 are each independently H or alkyl, or R 1 from the first L and R 1 from the second L together with the nitrogen atom and the metal atom to which each is attached form a heterocyclyl group as defined herein. In yet other embodiments, the formula is -OR 1 a first L that is and -OR 1 a second L that is, and R 1 are each independently H or alkyl, or R 1 from the first L and R 1 from the second L together with the oxygen atom and the metal atom to which each is attached form a heterocyclyl group as defined herein.

[0281] In some embodiments, at least one of L or R is optionally substituted alkyl. Non-limiting alkyl groups include, for example, C n H 2n+1 (where n is 1, 2, 3, or more), for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl, etc. In various embodiments, L or R has at least one β-hydrogen or β-halogen.

[0282] In some embodiments, at least one of L or R is optionally substituted haloalkyl. Non-limiting haloalkyl groups include, for example, C n H 2n+1-z Xz where n is 1, 2, 3, or more, z is from 1 to 2n + 1 (e.g., from 1 to 3, from 1 to 5, or from 1 to 7), and each X is independently a halo (F, Cl, Br, or I). In various embodiments, L or R has at least one β - hydrogen and / or β - halogen. In particular, the metal - containing precursor can be FCH2SnL3, CF3SnL3, ICH2SnL3, CI3SnL3, CH2FCH2SnL3, or CH2ICH2SnL3, and each L can be any of those described herein (e.g., including halo, optionally substituted amino, or optionally substituted alkoxy).

[0283] In some embodiments, at least one of L or R is an optionally substituted alkenyl or an optionally substituted alkynyl. Non - limiting examples of alkenyl groups include, for example, C n H 2n-1 (where n is 2, 3, 4, or more), such as ethenyl, 1 - propenyl, 2 - propenyl, 1 - butenyl, 2 - butenyl, or 3 - butenyl. Non - limiting examples of alkynyl groups include, for example, C n H 2n-3 (where n is 2, 3, 4, or more), such as ethynyl, 1 - propynyl, 2 - propynyl, 1 - butynyl, 2 - butynyl, or 3 - butynyl, etc.

[0284] There are various types of alkynyltin precursors used in dry resists. These precursors can react in different ways depending on the position of the carbon - carbon triple bond. When the carbon - carbon triple bond is not directly bonded to the tin center, for example, in the formula R 1 CCCH2SnL3 (R 1is a C1-C2 straight-chain or branched alkane such as methyl or ethyl, and L is an amino group (dimethylamino, diethylamino, ethylmethylamino, methylpropylamino, aminocyclopentane, aminocyclohexane) or an alkoxy group (methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, sec-butoxy, or n-butoxy). In this type of precursor, an unsaturated triple bond is expected to be incorporated into the film and cross-linked with other unsaturated groups.

[0285] Alkyne compounds having a carbon-carbon triple bond directly bonded to a tin atom hydrolyze in the presence of water, although much more slowly than amino and alkoxy groups. Thus, (R 1 C≡C)3SnR 2 and (R 1 C≡C)4Sn(R 1 is a simple alkane such as methyl or ethyl, and R 2 is a C1-C2 hydrocarbon) and other compounds are another way to introduce alkyl and groups into tin-oxo compounds. In the compound (R 1 C≡C)3SnR 2 the tin center has three alkynes, and the carbon-carbon triple bond is bonded to the tin center. These precursors react by a mechanism similar to that of the amino or alkoxysilane compounds described above, although the alkyne precursors may be thermally or hydrolytically more stable than the alkoxy or amino compounds. Due to the slow hydrolysis of the alkyne compounds, tetraalkynes such as those represented by (R 1 C≡C)4Sn may be used. When using (R 1 C≡C)4Sn, it may be possible to deposit a film containing a tin oxo network while maintaining to some extent the amount of cross-linkable alkyne groups in the film by controlling the ratio of water to the precursor.

[0286] In some embodiments, each L or at least one L is a halo. In particular, the metal-containing precursor can be a metal halide or an organometallic halide. Non-limiting metal halides and organometallic halides include FCH2SnX3, CF3SnX3, ICH2SnX3, CI3SnX3, CH2FCH2SnX3, CH2ICH2SnX3, SnX2, or SnX4, where each X is independently a halo. In other embodiments, the metal-containing precursor is RSnX3, where R is C 1-4 haloalkyl, C 2-4 haloalkenyl, or C 2-4 haloalkynyl, and each X is independently a halo. In yet other embodiments, the metal-containing precursor is RSnX3, where R is C 1-2 alkyl, C 2-4 alkenyl, or C 2-4 alkynyl, and each X is independently a halo.

[0287] In some embodiments, each L or at least one L can contain a nitrogen atom. In certain embodiments, one or more Ls can be optionally substituted amino or optionally substituted bis(trialkylsilyl)amino. Non-limiting L substitution components include, for example, -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)-(tbba), -N(SiMe3)2, and -N(SiEt3)2. Non-limiting metal-containing precursors include, for example, Sn(CH2F)(NMe2)3, Sn(CF3)(NMe2)3, Sn(CH2I)(NMe2)3, Sn(CI3)(NMe2)3, Sn(CH2CH2F)(NMe2)3, Sn(CH2CH2I)(NMe2)3, Sn(CH2F)2(NMe2)2, Sn(CF3)2(NMe2)2, Sn(CH2I)2(NMe2)2, Sn(CI3)2(NMe2)2, Sn(CH2CH2F)2(NMe2)2, Sn(CH2CH2I)2(NMe2)2, Sn(CH2F)(NEt2)3, Sn(CF3)(NEt2)3, Sn(CH2I)(NEt2)3, Sn(CI3)(NEt2)3, Sn(CH2CH2F)(NEt2)3, Sn(CH2CH2I)(NEt2)3, Sn(CH3)(NMe2)3, Sn(CH2CH3)(NMe2)3, Sn(CH=CH2)(NMe2)3, Sn(CH=CHCH3)(NMe2)3, Sn(CH2-CH=CH2)(NMe2)3, Sn(C≡CH)(NMe2)3, Sn(C≡CCH3)(NMe2)3, Sn(CH2C≡CH)(NMe2)3, Sn(NMe2)2, Sn(NEt2)2, or Sn[N(SiMe3)2]2.

[0288] In some embodiments, the metal-containing precursor is RSn(NMe2)3, RSn(NMe2)2(NEt2), RSn(NEt2)3, or RSn[N(SiMe3)2]3, where R is C 1-2 haloalkyl, C 2-4 haloalkenyl, C 2-4 haloalkynyl, C 1-2 alkyl, C 2-4 alkenyl, or C 2-4It is alkynyl. In other embodiments, the metal-containing precursor is R2Sn(NMe2)2, R2Sn(NMe2)(NEt2), R2Sn(NEt2)2, or R2Sn[N(SiMe3)2]2, where each R is independently C 1-2 haloalkyl, C 2-4 haloalkenyl, C 2-4 haloalkynyl, C 1-2 alkyl, C 2-4 alkenyl, or C 2-4 alkynyl.

[0289] In other embodiments, the metal-containing precursor is RSnL3, where R is C 1-2 haloalkyl, C 2-4 haloalkenyl, C 2-4 haloalkynyl, C 1-2 alkyl, C 2-4 alkenyl, or C 2-4 alkynyl, and each L is independently selected from the group consisting of -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)-(tbba), -N(SiMe3)2, and N(SiEt3)2.

[0290] In other embodiments, the metal-containing precursor is RSnL3, where R is C1-C3 aliphatic (wherein the C1-C3 aliphatic may be optionally substituted with a ketone, an alkoxy group, or an epoxy group) or a -C(O)C1-C3 alkyl group, and each L is independently selected from the group consisting of an optionally substituted alkoxy, -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)-(tbba), -N(SiMe3)2, and N(SiEt3)2. Ether, ketone, or epoxide-containing R groups on the metal-containing precursor may be advantageous for assisting in crosslinking.

[0291] In yet other embodiments, the metal-containing precursor is SnL2, and each L is independently selected from the group consisting of -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)-(tbba), -N(SiMe3)2, and -N(SiEt3)2.

[0292] In some embodiments, each L or at least one L can contain a silicon atom. In certain embodiments, one or more Ls can be an optionally substituted trialkylsilyl or an optionally substituted bis(trialkylsilyl). Non-limiting L substitution components include, for example, -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2. Non-limiting metal-containing precursors include, for example, Sn[N(SiMe3)2]2, bis(trimethylsilyl)tellurium (Te(SiMe3)2), bis(triethylsilyl)tellurium (Te(SiEt3)2), or Bi[N(SiMe3)2]3.

[0293] In some embodiments, each L or at least one L can contain an oxygen atom. In certain embodiments, one or more Ls can be an optionally substituted alkoxy. Non-limiting L substitution components include, for example, methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), and -O=C(CH3)-CH=C(CH3)-O-(acac). Non-limiting metal-containing precursors include, for example, Sn(CH2F)(t-BuO)3, Sn(CF3)(t-BuO)3, Sn(CH2I)(t-BuO)3, Sn(CI3)(t-BuO)3, Sn(CH2CH2F)(t-BuO)3, Sn(CH2CH2I)(t-BuO)3, Sn(CH2F)2(t-BuO)2, Sn(CF3)2(t-BuO)2, Sn(CH2I)2(t-BuO)2, Sn(CI3)2(t-BuO)2, Sn(CH2CH2F)2(t-BuO)2, Sn(CH2CH2I)2(t-BuO)2, Sn(t-BuO)2, Sn(CH3)(t-BuO)3, Sn(CH2CH3)(t-BuO)3, Sn(CH=CH2)(t-BuO)3, Sn(CH=CHCH3)(t-BuO)3, Sn(CH2-CH=CH2)(t-BuO)3, Sn(C≡CH)(t-BuO)3, Sn(C≡CCH3)(t-BuO)3, Sn(CH2C≡CH)(t-BuO)3, or Sn(acac)2.

[0294] In some embodiments, the metal-containing precursor is RSn(t-BuO)3, where R is C 1-2 haloalkyl, C 2-4 haloalkenyl, C 2-4 haloalkynyl, C 1-2 alkyl, C 2-4 alkenyl, or C 2-4 alkynyl. In other embodiments, the metal-containing precursor is R2Sn(t-BuO)2, where each R is independently C 1-2 haloalkyl, C 2-4 haloalkenyl, C 2-4 haloalkynyl, C 1-2 alkyl, C 2-4 alkenyl, or C 2-4 alkynyl. In yet other embodiments, the metal-containing precursor is RSnL3, where R is C 1-2 haloalkyl, C 2-4 haloalkenyl, C 2-4 haloalkynyl, C 1-2 alkyl, C 2-4 alkenyl, or C 2-4 alkynyl, and each L is independently selected from the group consisting of methoxy, ethoxy, i-PrO, and t-BuO.

[0295] To provide a non-limiting example of a film, a ligand-containing precursor can be employed to react with the metal-containing precursor or replace the ligand of the metal-containing precursor. Non-limiting ligand-containing precursors are described herein.

[0296] Such precursor(s) can further be used in combination with one or more counterreactants. The counterreactant preferably has the ability to replace a reactive site, ligand, or ion (e.g., L in the various formulas herein) so as to link at least two metal atoms via a chemical bond. Exemplary counterreactants include oxygen-containing counterreactants such as O2, O3, water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, dihydroxy alcohols or polyhydroxy alcohols, fluorinated dihydroxy alcohols or fluorinated polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl sites, and combinations thereof. In various embodiments, the counterreactant reacts with the metal-containing precursor and / or ligand-containing precursor by forming an oxygen bridge between adjacent metal atoms. Other potential counterreactants include hydrogen sulfide and hydrogen disulfide that can bridge metal atoms via sulfur bridges, and bis(trimethylsilyl) tellurium that can bridge metal atoms via tellurium bridges. Further, hydrogen iodide may be utilized to incorporate iodine into the film.

[0297] In certain embodiments, the counterreactant is a chalcogenide precursor and includes, for example, a structure having the following formula: Formula X 3 -Z-X 4 (Z is sulfur, selenium, or tellurium, X 3 and X 4 are each independently H, optionally substituted alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc.), optionally substituted alkenyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or optionally substituted trialkylsilyl.)

[0298] Gradient films can be formed using the metal-containing precursors of this specification. For example, the various atoms present in the metal-containing precursor, the ligand-containing precursor, and / or the counter-reagent can be provided within the gradient film. In some embodiments of the techniques discussed herein, a non-limiting strategy for further improving EUV sensitivity in a photoresist (PR) film is to create a film whose film composition has a vertical gradient and as a result has depth-dependent EUV sensitivity. In a homogeneous PR with a high absorption coefficient, since the light intensity decreases throughout the film depth, it is necessary to increase the EUV dose so that the bottom is sufficiently exposed. By increasing the density of atoms with a high EUV absorption rate at the bottom of the film relative to the top of the film (i.e., creating a gradient where EUV absorption increases), it becomes possible to distribute absorption (and the effect of secondary electrons) more uniformly towards the film bottom with a higher absorption rate while using the available EUV photons more efficiently. In a non-limiting example, the gradient film contains Te, I, or other atoms towards the bottom of the film (e.g., the side closer to the substrate).

[0299] The strategy of designing a vertical composition gradient in a PR film is applicable in particular to dry deposition methods such as CVD and ALD and can be realized by adjusting the flow rate ratio between different reagents during deposition. Examples of the types of compositional gradients that can be designed include the ratio between different high-absorption metals, the proportion of metal atoms having an EUV-cleavable organic group, the proportion of (halo)aliphatic substitution components and / or counter-reagents containing high-absorption elements, and combinations of the above.

[0300] The compositional gradient of the EUV PR film can also bring further benefits. For example, by increasing the density of the high ultraviolet-absorbing elements at the bottom of the film, more secondary electrons can be effectively generated, and the secondary electrons can expose the upper part of the film better. Further, such a compositional gradient can also be directly correlated with a high proportion of EUV-absorbing species not bound to bulky end-substituted components. For example, in the case of Sn-based resists, it is possible to incorporate tin precursors having four leaving groups, thereby promoting the formation of Sn-O-substrate bonds at the interface and improving the adhesion.

[0301] Such gradient films can be formed using any of the metal-containing precursors (e.g., tin or non-tin precursors), ligand-containing precursors, and / or counter-reagents described herein. Further other films, methods, precursors, and other compounds are described in U.S. Provisional Patent Application No. 62 / 909,430, filed Oct. 2, 2019, entitled "SUBSTRATE SURFACE MODIFICATION WITH HIGH EUV ABSORBERS FOR HIGH PERFORMANCE EUV PHOTORESISTS", and International Application PCT / US20 / 70172, filed Jun. 24, 2020, entitled "PHOTORESIST WITH MULTIPLE PATTERNING RADIATION-ABSORBING ELEMENTS AND / OR VERTICAL COMPOSITION GRADIENT", the disclosures of which, including at least the composition, deposition, and patterning of the directly photopatternable metal oxide film for forming an EUV resist mask, are hereby incorporated herein by reference.

[0302] Furthermore, two or more different precursors can be employed within each layer (e.g., film or capping layer). For example, two or more of any of the metal-containing precursors herein can be employed to form an alloy. In one non-limiting example, tin telluride can be formed by employing 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 can be formed by 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).

[0303] Further exemplary EUV-sensitive materials, as well as processing methods and apparatuses, are described in U.S. Patent No. 9,996,004 and International Publication WO2019 / 217749, which are each incorporated herein by reference in their entirety.

[0304] Ligand-containing precursor The ligand-containing precursor can be anything having a ligand (e.g., reactive with respect to a counter-reagent and / or a metal-containing precursor). In one embodiment, such ligand-containing chemicals are typically employed prior to a film deposition process for preparing the appropriate metal-containing precursor.

[0305] In certain embodiments, the ligand-containing precursor is an organolithium compound (e.g., LiL), an organosodium compound (e.g., NaL), an organomagnesium compound (e.g., MgL2), a Grignard reagent (e.g., MgLX where X is halo), an organozinc compound (e.g., ZnL2), or an organoaluminum compound (e.g., AlL3).

[0306] In another embodiment, the ligand-containing precursor can be employed to synthesize the precursor (prior to deposition) or to provide the precursor in situ (e.g., during deposition in a chamber). In some embodiments, the metal-containing precursor contains tin(II).

[0307] Examples of other ligand-containing precursors include organolithium compounds such as lithium dimethylamide [LiNMe2] and lithium bis(trimethylsilyl)amide [LiN(SiMe3)2].

[0308] Still other ligand-containing precursors include aluminum halides such as aluminum bromide [AlBr3] and aluminum chloride [AlCl3]; organoaluminum compounds including trialkylaluminum and triaryl aluminum such as trimethylaluminum [AlMe3] and triethylaluminum [AlEt3]; aluminum alkoxides such as aluminum methoxide [Al(OMe)3] and aluminum i-propoxide [Al(OiPr)3]; and tris(dialkylamide)aluminum such as tris(dimethylamide)aluminum [Al(NMe2)3 or Al2(NMe2)6].

[0309] Still other ligand-containing precursors include haloalkyl halides or alkyl halides, such as iodo haloalkyl, bromo haloalkyl, chloro haloalkyl, fluoro haloalkyl, iodoalkyl, bromoalkyl, chloroalkyl, or fluoroalkyl. In some embodiments, the haloalkyl is -CX y H 3-y (where y is 1, 2, or 3 and each X is independently halo (F, Cl, Br, or I)); -CX z H 2-z CX y H 3-y (where z is 0, 1, or 2, y is 0, 1, 2, or 3, each X is independently halo (F, Cl, Br, or I), and at least one of z or y is not 0); -CH2CX y H 3-y (where y is 1, 2, or 3 and each X is independently halo (F, Cl, Br, or I)); or C n H 2n+1-z X z(n is 1, 2, 3, or more, z is 1 to 2n + 1 (for example, 1 to 3, 1 to 5, or 1 to 7), and each X is independently halo (F, Cl, Br, or I)). Further non-limiting haloalkyl groups include halo-substituted methyl containing 1, 2, or 3 halo substitution components, etc. described herein, halo-substituted ethyl containing 1, 2, or 3 halo substitution components, and β-halo-substituted ethyl containing 1, 2, or 3 halo substitution components (for example, those described herein). In other embodiments, the alkyl is -C n H 2n+1 (n is 1 or 2), -C n H 2n-1 (n is 2, 3, or 4), or -C n H 2n-3 (n is 2, 3, or 4).

[0310] Additional Precursors As described herein, the films, layers, and methods herein can be employed with any useful precursor. The following precursors can be used as metal-containing precursors or ligand-containing precursors.

[0311] Non-limiting tin precursors include SnF2, SnH4, SnBr4, SnCl4, SnI4, tetramethyltin (SnMe4), tetraethyltin (SnEt4), trimethyltin chloride (SnMe3Cl), dimethyltin dichloride (SnMe2Cl2), methyltin trichloride (SnMeCl3), tetraallyltin, tetravinyltin, hexaphenylditin(IV) (Ph3Sn-SnPh3 where Ph is phenyl), dibutyldiphenyltin (SnBu2Ph2), trimethyl(phenyl)tin (SnMe3Ph), trimethyl(phenylethynyl)tin, tricyclohexyltin hydride, tributyltin hydride (SnBu3H), dibutyltin diacetate (SnBu2(CH3COO)2), tin(II) acetylacetonate (Sn(acac)2), SnBu3(OEt), SnBu2(OMe)2, SnBu3(OMe), Sn(t-BuO)4, Sn(n-Bu)(t-BuO)3, tetrakis(dimethylamino)tin (Sn(NMe2)4), tetrakis(ethylmethylamino)tin (Sn(NMeEt)4), tetrakis(diethylamino)tin(IV) (Sn(NEt2)4), (dimethylamino)trimethyltin(IV) (Sn(Me)3(NMe2), Sn(i-Pr)(NMe2)3, Sn(n-Bu)(NMe2)3, Sn(s-Bu)(NMe2)3, Sn(i-Bu)(NMe2)3, Sn(t-Bu)(NMe2)3, Sn(t-Bu)2(NMe2)2, Sn(t-Bu)(NEt2)3, Sn(tbba), Sn(II)(1,3-bis(1,1-dimethylethyl)-4,5-dimethyl-(4R,5R)-1,3,2-diazastannolidine-2-ylidene), or bis[bis(trimethylsilyl)amino]tin (Sn[N(SiMe3)2]2).

[0312] Exemplary organometallic agents include SnMeCl3, (N 2 ,N 3-Di-t-butyl-butane-2,3-diamide)tin(II) (Sn(tbba)), bis(bis(trimethylsilyl)amide)tin(II), tetrakis(dimethylamino)tin(IV) (Sn(NMe2)4), t-butyltris(dimethylamino)tin (Sn(t-butyl)(NMe2)3), i-butyltris(dimethylamino)tin (Sn(i-Bu)(NMe2)3), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe2)3), sec-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe2)3), i-propyl(tris)dimethylaminotin (Sn(i-Pr)(NMe2)3), n-propyltris(diethylamino)tin (Sn(n-Pr)(NEt2)3), and similar alkyl(tris)(t-butoxy)tin compounds, such as t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO)3). In some embodiments, the organometallic agent is partially fluorinated.

[0313] Lithography process In EUV lithography, EUV resists are used, which may be polymer-based chemically amplified resists produced by liquid-based spin-on techniques, or metal oxide-based resists produced by dry deposition techniques. Such EUV resists can include any of the EUV-sensitive films or materials described herein. The lithography method can include exposing the EUV resist with EUV radiation to form a photopattern, and then developing the pattern to remove a portion of the resist according to the photopattern to form a mask.

[0314] Note that although the present disclosure relates to lithography patterning techniques and materials exemplified in EUV lithography, it should be understood that it is also applicable to other next-generation lithography techniques. In addition to EUV with the standard 13.5 nm EUV wavelength currently in use and development, the radiation sources most relevant to such lithography generally refer to DUV (deep ultraviolet), which uses an excimer laser source of 248 nm or 193 nm, X-rays, which formally include EUV in the lower energy range of the X-ray range, and electron beams capable of covering 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 of those described herein) to form a metal oxide (e.g., a layer containing a network of metal oxide bonds and which may also contain other non-metal and non-oxygen groups) film as an imaging / photoresist (PR) layer on the surface of the substrate. The specific method may depend on the specific materials and applications used in semiconductor substrates and final semiconductor devices. Accordingly, the methods described in this application are merely illustrative of methods and materials that may be used in this technology.

[0315] EUV resists that are directly photopatternable are composed of, or may contain, metals and / or metal oxides mixed in an organic component. Metals / metal oxides are promising in that they can enhance the adsorption of EUV photons, generate secondary electrons, and / or increase the etching selectivity with respect to the underlying film stack and device layers. So far, these resists have been developed using a wet (solvent) approach, which requires moving the wafer to a track where it is exposed to a developing solvent, dried, and baked. Wet development not only limits productivity but also has the potential to cause line collapse due to surface tension effects when the solvent evaporates between fine features.

[0316] Dry development techniques have been proposed to overcome these problems by eliminating delamination and interfacial failures of the substrate. Dry development has unique challenges, including the etching selectivity between the unexposed resist material and the EUV-exposed resist material, and the dose to size for effective resist exposure can be higher compared to wet development. Also, sub-optimal selectivity can cause rounding of the PR angle due to prolonged exposure under the etching gas, which can lead to increased line CD variation in the next transfer etching step. The additional processes employed during lithography are described in detail below.

[0317] Deposition processes including dry deposition As described above, what the present disclosure provides is a method for fabricating an imaging layer on a semiconductor substrate, which may be patterned using EUV or other next-generation lithography techniques. The method includes generating a polymerized organometallic material in a vapor and depositing it on the substrate. In some embodiments, in dry deposition, any useful metal-containing precursor (e.g., metal halides, capping agents, or organometallic agents described herein) may be employed. In other embodiments, a spin-on process may be used. The deposition process can include applying an EUV-sensitive material as a resist film and / or as a capping layer on top of the resist film. Exemplary EUV-sensitive materials are described herein.

[0318] The present technology includes a method of depositing an EUV-sensitive film on a substrate, such a film can function as a resist for subsequent EUV lithography and processing. Further, an EUV-sensitive secondary film can be deposited on top of the underlying EUV-sensitive primary film. In one example, the secondary film constitutes a capping layer and the primary film constitutes an imaging layer.

[0319] Such EUV-sensitive films comprise materials that, when exposed to EUV, undergo changes such as the loss of bulky pendant ligands bonded to metal atoms in a low-density M-OH-rich material, enabling crosslinking to a higher-density M-O-M-bonded metal oxide material. In other embodiments, as a result of EUV exposure, further crosslinking occurs between the ligands bonded to the metal atoms, providing a higher-density M-L-M-bonded organometallic material (where L is a ligand). In still other embodiments, as a result of EUV exposure, ligands are lost, providing an M-OH material that can be removed with a positive-tone developer.

[0320] EUV patterning creates a region of the film whose physical or chemical properties are changed compared to the unexposed region. These properties may be exploited in subsequent processing, such as dissolving either the unexposed or exposed region, or selectively depositing material on either the exposed or unexposed region. In some embodiments, under the conditions under which such subsequent processing is carried out, the unexposed film has a hydrophobic surface and the exposed film has a hydrophilic surface (the hydrophobicity of the exposed and unexposed regions is recognized as being relative to each other). For example, removal of the material may be carried out by taking advantage of differences in the chemical composition, density, and crosslinking of the film. Removal may be carried out by wet or dry processing, as further described herein.

[0321] The thickness of the EUV-patternable film formed on the surface of the substrate may vary depending on the surface properties, the materials used, and the processing conditions. In various embodiments, the film thickness may be in the range of about 0.5 to 100 nm. Preferably, the film has a thickness sufficient to absorb most of the EUV light under the conditions of EUV patterning. For example, the overall absorption of the resist film may be 30% or less (e.g., 10% or less, or 5% or less), whereby the resist material at the bottom of the resist film is sufficiently exposed. In some embodiments, the film thickness is 10 to 20 nm. Without limiting the mechanisms, functions, or utilities of the present disclosure, unlike wet spin coating processes in the art, the processes of the present disclosure are considered applicable to a wide variety of substrates because they have fewer constraints on the surface adhesion properties of the substrate. Further, as described above, the deposited film may fit perfectly to the features on the surface, thereby providing advantages without "filling" such features or flattening them in other ways when forming a mask on a substrate such as a substrate having underlying features.

[0322] The film (e.g., imaging layer) or capping layer may be composed of a metal oxide layer deposited by any useful method. Such a metal oxide layer can be deposited or applied by using any of the EUV-sensitive materials described herein, such as a metal-containing precursor (e.g., metal halide, capping agent, or organometallic agent) combined with an optional ligand-containing precursor. In an exemplary process, a polymeric organometallic material is formed in the gas phase or in situ on the surface of the substrate to provide the metal oxide layer. The metal oxide layer may be employed as a film, an adhesive layer, or a capping layer.

[0323] Optionally, the metal oxide layer can include a hydroxyl-terminated metal oxide layer, which can be deposited by employing a capping agent (e.g., any of those described herein) with an oxygen-containing reactant. Such a hydroxyl-terminated metal oxide layer can be employed, for example, as an adhesion layer between two other layers such as between a substrate and a film and / or between a photoresist layer and a capping layer.

[0324] Exemplary deposition techniques (e.g., for a film or a capping layer) include any of those described herein, for example, ALD (e.g., thermal ALD and plasma-enhanced ALD), spin-coat deposition, PVD including PVD cosputtering, CVD (e.g., PE-CVD or LP-CVD), sputter deposition, electron beam deposition including electron beam co-evaporation, etc., or combinations thereof, such as ALD with CVD components like a discontinuous ALD-like process where a metal-containing precursor, a ligand-containing precursor, and a reactant are spatially or temporally separated.

[0325] The deposition method of a tin-based EUV resist is, in some embodiments, to react tetrakis(dimethylamino)tin with acetamide in the gas phase. The acetamide reagent replaces the amine groups on tin to produce a tin complex Sn(NR’C(O)R)4. In certain embodiments, the central tin atom is six-coordinate, and two of the acetamide ligands are bidentate-coordinated and two are monodentate-coordinated. When exposed to EUV radiation and secondary electrons, the acetamide ligands decompose and begin to form Sn-O-Sn bonds. R and R’ are each independently H, a C1-C7 straight-chain, branched, or cyclic alkane, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, or benzyl. Useful acetamides include acetamide, N-methylacetamide, N-ethylacetamide, N-methylformamide, N-ethylformamide, N-methylpropionamide, or propionamide.

[0326] Further description of the precursor as an EUV photoresist film applicable to the present disclosure and its deposition method can be found in International Application PCT / US19 / 31618. This was published as International Publication WO2019 / 217749, filed on May 9, 2019, and titled "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS". The thin film may change the chemical or physical properties of the film, such as changing the sensitivity of the film to EUV or enhancing the etching resistance, by including an optional material in addition to the metal-containing precursor, the ligand-containing precursor, and the counter-reagent. The introduction of such an optional material may be carried out, for example, by dosing during the gas-phase formation before deposition on the substrate, after deposition of the film, or both. In some embodiments, a gentle remote H2 plasma may be introduced to replace a part of the Sn-L bond with Sn-H, which can, for example, enhance the reactivity of the resist under EUV.

[0327] Typically, the method can include mixing a vapor stream of an organometallic precursor (e.g., a metal-containing precursor such as an organometallic agent) with an optional vapor stream of a ligand-containing precursor and an optional vapor stream of a counter-reagent to form a polymerized organometallic material, and depositing the organometallic material on the surface of a semiconductor substrate. In some embodiments, a polymerized organometallic material can be formed by mixing a metal-containing precursor with an optional ligand-containing precursor and an optional counter-reagent. As those skilled in the art will understand, the mixing and deposition aspects of this process may be used simultaneously in a substantially continuous process.

[0328] In an exemplary continuous CVD process, two or more gas streams in separate inlet channels of a metal-containing precursor, an optional ligand-containing precursor, and an optional co-reactant source are introduced into the deposition chamber of the CVD apparatus, where they are mixed and reacted in the gas phase to form an aggregated polymeric material (e.g., via metal-oxygen-metal bond formation) or a film on a substrate. The gas streams may be introduced, for example, using separate injection ports or a dual-plenum showerhead. The apparatus is configured such that the flows of the metal-containing precursor, the optional ligand-containing precursor, and the optional co-reactant are mixed within the chamber, whereby the metal-containing precursor, the optional ligand-containing precursor, and the optional co-reactant react to form a polymeric organometallic material or a film (e.g., a metal oxide coating or an aggregated polymeric material such as via metal-oxygen-metal bond formation).

[0329] When depositing a metal oxide, the CVD process is typically carried out under reduced pressure, e.g., 0.1 to 10 Torr. In some embodiments, the process is carried out at a pressure of 1 to 2 Torr. The temperature of the substrate is preferably lower than the temperature of the reaction stream. For example, the substrate temperature may be 0 to 250 °C, or ambient temperature (e.g., 23 °C) to 150 °C.

[0330] When depositing an aggregated polymeric material, the CVD process is typically carried out under reduced pressure, e.g., 10 mTorr to 10 Torr. In some embodiments, the process is carried out at 0.5 to 2 Torr. The temperature of the substrate is preferably the same as or lower than the temperature of the reaction stream. For example, the substrate temperature may be 0 to 250 °C, or ambient temperature (e.g., 23 °C) to 150 °C. In various processes, the deposition of the polymeric organometallic material onto the substrate occurs at a rate inversely proportional to the surface temperature. Without limiting the mechanism, function, or utility of the present technology, it is believed that products from such gas-phase reactions become heavier in molecular weight as metal atoms are cross-linked by the ligand-containing precursor and / or co-reactant, and then condense or deposit onto the substrate in another way.

[0331] A potential advantage of using dry deposition methods is that the composition can be easily adjusted as the film grows. In a CVD process, this may be achieved by varying the relative flow rates of the metal-containing precursor and the ligand-containing precursor during deposition. Deposition can occur at 30 - 200 °C and at 0.01 - 100 Torr, although more typically at a pressure of about 0.1 - 10 Torr.

[0332] A film (e.g., a metal oxide coating or an aggregated polymeric material, such as formed via metal-oxygen-metal bond formation) may also be deposited by an ALD process. For example, the metal-containing precursor, optional ligand-containing precursor, and optional counter-reactant are introduced at separate times representing an ALD cycle. The metal-containing precursor and optional ligand-containing precursor react on the surface to form a maximum of one layer of material per cycle. This may enable skillful control of the uniformity of the film thickness across the entire surface. The ALD process is typically carried out under reduced pressure, e.g., 0.1 - 10 Torr. In some embodiments, the process is carried out at 1 - 2 Torr. The substrate temperature may be 0 - 250 °C, or ambient temperature (e.g., 23 °C) - 150 °C. The process may be a thermal process, and preferably may be plasma-assisted deposition.

[0333] Any of the deposition methods herein can be modified to allow for the use of two or more different metal-containing precursors. In one embodiment, each precursor can contain the same metal but different ligands. In another embodiment, each precursor can contain different metal groups. As a non-limiting example, a mixed metal layer can be provided, such as by flowing various volatile metal-containing precursors alternately, using a metal alkoxide precursor having a first metal (e.g., Sn) together with a silyl-based precursor having a different second metal (e.g., Te).

[0334] Also, any of the deposition methods described herein can be modified to allow the use of two or more different ligand-containing precursors. In one embodiment, the ligand-containing precursors can provide different binding ligands to the metal center. As a non-limiting example, by flowing various ligand-containing precursors alternately, a layer with a varying ligand content can be provided, such as in a gradient film.

[0335] Furthermore, any of the deposition methods described herein can be modified to provide one or more layers within a film or capping layer. In one example, different metal-containing precursors and / or ligand-containing precursors can be employed for each layer. In another example, the same precursors can be used for each layer, but the top layer can have a different chemical composition (e.g., different density of metal-ligand bonds, different ratio of metal to carbon, different halogen content, or different binding ligands provided by adjusting or varying the metal or ligand-containing precursors).

[0336] Using the processes described herein, surface modification can be achieved. In some iterative procedures, the vapor of the metal-containing precursor can pass over the wafer. The wafer can be heated to provide the thermal energy for the reaction to proceed. In some iterative procedures, the heating can be performed at about 50 - 250 °C. In some cases, pulses of the metal and / or ligand-containing precursors can be separated and used by means of pumping and / or purge steps. As an example, the ligand-containing precursor can be pulsed between precursor pulses to result in ALD or ALD-like growth. In other cases, both the metal precursor and the ligand-containing precursor can be flowed simultaneously. Examples of elements useful for surface modification include I, F, Sn, Bi, Sb, Te, and oxides or alloys of these compounds.

[0337] Using the processes described herein, thin metal oxides or metals can be deposited by ALD or CVD. Examples include SnOx, BiOx, and Te. Following deposition, the film can be treated with a haloalkyl-substituted precursor or M a R b Lc It may be capped with an alkyl-substituted precursor in the form. A counteragent may be used to better remove the ligand, and multiple cycles may be repeated to ensure complete saturation of the substrate surface. Here, the surface is in a state where an EUV-sensitive film can be deposited. One possible method is to generate a thin film of SnOx. Possible chemical reactions include the growth of SnO2 by circulating tetrakis(dimethylamino)tin and a counteragent such as water or O2 plasma. After growth, a capping agent can also be used. For example, the vapor of isopropyltris(dimethylamino)tin may be sprayed onto the surface.

[0338] The deposition process can be employed on any useful surface. The "surface" referred to in this specification is the surface on which the film of the present technology is deposited or the surface that is exposed to EUV during processing. Such a surface can exist on a substrate (e.g., on which a film is deposited), on a film (e.g., on which a capping layer is deposited), or on a capping layer.

[0339] Any useful substrate can be employed, including a lithography process, particularly a material composition suitable for the production of integrated circuits and other semiconductor devices. In some embodiments, the substrate is a silicon wafer. The substrate may be a silicon wafer having features with an irregular surface topography ( "underlying topographical features") formed thereon.

[0340] Such underlying topographical features may include areas where material has been removed (e.g., by etching) or added (e.g., by deposition) during a process preceding the implementation of the method of the present technology. Such preceding processes may include the method of the present technology or other processing methods in an iterative process of forming two or more layers of features on a substrate. Without limiting the mechanism, function, or utility of the present technology, in some embodiments, the method of the present technology is considered to provide advantages compared to methods known in the art for depositing a photolithography film on the surface of a substrate using a spin-casting method. Such advantages may result from the film of the present technology conforming to underlying features without "filling" such features or otherwise planarizing them, and from the ability to deposit the film on a wide variety of material surfaces.

[0341] In some embodiments, the incoming wafer can be prepared using a substrate surface of a desired material, and the topmost material is the layer onto which the resist pattern is transferred. The material selection may vary depending on the integration, and it is usually desirable to select a material that can be etched with high selectivity (i.e., much faster) with respect to an EUV resist or imaging layer. Suitable substrate materials can include various carbon-based films (e.g., an ashingable hard mask (AHM)), silicon-based films (e.g., silicon, silicon oxide, silicon nitride, silicon oxynitride, or silicon carbonitride, and these doped forms including SiO x 、SiO x N y 、SiO x C y N z 、a-Si:H, poly-Si, or SiN in these doped forms), or other (usually sacrificial) films applied to facilitate the patterning process.

[0342] In some embodiments, the substrate is a hard mask, which is used for lithographic etching of underlying semiconductor materials. The hard mask can be amorphous carbon (a-C), SnO x, SiO2, SiO x N y , SiO x C, Si3N4, TiO2, TiN, W, W-doped C, WO x , HfO2, ZrO2, and Al2O3, etc., may include any of a variety of materials. For example, the substrate preferably includes SnO such as SnO2, etc. x In various embodiments, the layer may have a thickness of 1 to 100 nm, or a thickness of 2 to 10 nm.

[0343] In some non-limiting embodiments, the substrate includes an underlayer. The underlayer may be deposited on the hard mask or on other layers and is usually under the imaging layer (or film) as described herein. The underlayer may be used to improve the sensitivity of the PR, increase the EUV absorption rate, and / or enhance the patterning performance of the PR. When there are device features on the substrate to be patterned and they form a large topography, another important function of the underlayer is to coat and flatten the existing topography so that subsequent patterning steps can be performed with focus on a flat surface over the entire range of the pattern. In such applications, the underlayer (or at least one of the plurality of underlayers) may be applied using spin coating techniques. If the PR material employed has important inorganic components such as mainly showing a metal oxide backbone, the underlayer may advantageously be a carbon-based film deposited either by spin coating or by a dry vacuum-based deposition process. This layer may include various ashing hard mask (AHM) films having a carbon-based composition and a hydrogen-based composition, and may be doped with additional elements such as tungsten, boron, nitrogen, or fluorine.

[0344] In some embodiments, a surface activation operation may be used to activate the surface (e.g., of the substrate and / or the film) for future operations. For example, SiO xIn the case of the surface, hydroxyl groups may be generated on the surface using water or oxygen / hydrogen plasma. In the case of a carbon-based or hydrocarbon-based surface, various treatments (e.g., treatment with water, hydrogen / oxygen, CO2 plasma, or ozone) may be used to generate carboxylic acid / or hydroxyl groups. Such an approach can be proven to be extremely important in improving the adhesion of resist features to the substrate, where in other ways, they may peel off or lift off in the solvent during handling or development.

[0345] Adhesion may also be enhanced by inducing roughness on the surface, increasing the surface area available for interaction, and directly improving mechanical adhesion. For example, a rough surface can be generated using a sputtering process that first uses an impact of Ar or other non-reactive ions. Next, the surface can be terminated with the desired surface functional groups described above (e.g., hydroxyl groups and / or carboxylic acid groups). On carbon, a combined approach can be employed where a thin film layer with local inhomogeneities is etched away using a chemically reactive oxygen-containing plasma such as CO2, O2, H2O (or a mixture of H2 and O2), while simultaneously terminating with -OH groups, -OOH groups, or -COOH groups. This may be done with or without bias. When combined with the surface modification strategies described above, this approach can serve two purposes: roughening and chemical activation of the substrate surface, either for direct adhesion to an inorganic metal oxide-based resist or as an intermediate surface modification for further functionalization.

[0346] In various embodiments, the surface (e.g., of a substrate and / or a film) includes hydroxyl groups exposed on the surface. Typically, the surface may be any surface that includes an exposed hydroxyl surface or is 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 can be treated to provide exposed hydroxyl groups onto which a capping layer can be applied. In various embodiments, the hydroxyl-terminated metal oxide layer has a thickness of 0.1 to 20 nm, or 0.2 to 10 nm, or 0.5 to 5 nm.

[0347] EUV exposure process EUV exposure of the film can provide an EUV exposure region having activated reaction centers that include metal atoms (M) generated by EUV-mediated cleavage events. Such reaction centers include dangling metal bonds, M-H groups, cleaved M-ligand groups, dimerized M-M bonds, or M-O-M bridges. In other embodiments, EUV exposure provides crosslinked organic sites by photopolymerizing ligands within the film, or EUV exposure releases gaseous by-products resulting from photolysis of bonds within the ligands.

[0348] EUV exposure can have a wavelength in the range of about 10 to 20 nm, such as a wavelength of 10 to 15 nm, or such as a wavelength of 13.5 nm, in a vacuum environment. In particular, patterning can provide an EUV exposure region and an EUV unexposed region for forming a pattern.

[0349] The present technology can include patterning using EUV, and DUV or an electron beam. In such patterning, radiation is focused on one or more regions of an imaging layer. The exposure is typically performed such that the imaging layer film includes one or more regions that are not exposed to the radiation. The resulting imaging layer may include a plurality of exposed regions and unexposed regions, which create a pattern that corresponds to the creation of transistors or other features of a semiconductor device and is formed by adding or removing material from the substrate in subsequent processing of the substrate. Methods and apparatuses for EUV, DUV, and electron beam radiation useful herein include those known in the art.

[0350] In some EUV lithography techniques, an organic hard mask (e.g., an ashingable hard mask of PECVD amorphous hydrogenated carbon) is patterned using a conventional photoresist process. During photoresist exposure, EUV radiation is absorbed by the resist and the underlying substrate, generating high-energy photoelectrons (e.g., about 100 eV), which in turn sequentially generate low-energy secondary electrons (e.g., about 10 eV) that diffuse laterally by several nanometers. These electrons enhance the degree of chemical reaction in the resist and increase the sensitivity to EUV dose. However, an essentially random pattern of secondary electrons is superimposed on the optical image. As a result of this unwanted secondary electron exposure, resolution is lost, and line edge roughness (LER) and line width variations observable in the patterned resist occur. These defects are repeated in the material to be patterned during subsequent pattern transfer etching.

[0351] Disclosed herein is a vacuum integrated metal hard mask process and associated vacuum integrated hardware that combines film formation (deposition / condensation) and optical lithography, resulting in significantly improved EUV lithography (EUVL) performance (e.g., reduced line edge roughness).

[0352] In various embodiments described herein, a deposition (e.g., condensation) process (e.g., ALD or MOCVD implemented in a PECVD tool such as Lam Vector™) is used to form a metal-containing film, such as a photosensitive metal salt or a metal-containing organic compound (organometallic compound), which has a strong absorption rate for EUV (e.g., wavelengths on the order of 10 - 20 nm) at the wavelength of an EUVL light source (e.g., 13.5 nm = 91.8 eV). This film undergoes photolysis when exposed to EUV light and forms a metal mask, which is a pattern transfer layer, during subsequent etching (e.g., in a conductor etching tool such as Lam2300™ Kiyo™).

[0353] Subsequent to deposition, the EUV-patternable thin film is typically patterned by exposure to a beam of EUV light under a relatively high vacuum. In the case of EUV exposure, 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 platform provided by ASML of Veldhoven, Netherlands) and transferred under vacuum so as not to react prior to exposure. The integration with the lithography tool is driven by the fact that even EUVL requires a significant pressure reduction due to the strong light absorption of incident photons by ambient gases such as H2O, O2. In other embodiments, the photosensitive metal film deposition and EUV exposure may be performed in the same chamber.

[0354] A development process including dry development The EUV-exposed or unexposed areas, and the capping layer, can be removed by any useful development process. In one embodiment, the EUV-exposed area can have activated reaction centers such as dangling metal bonds, M-H groups, or dimerized M-M bonds. In certain embodiments, the M-H groups can be selectively removed by employing one or more dry development processes (e.g., halide chemical reactions). In other embodiments, the M-M bonds can be removed by a wet development process, such as soluble M(OH) nIt can be selectively removed by adopting the use of high-temperature ethanol and water to provide a base. Further, in other embodiments, the EUV exposure area is removed by using wet development (e.g., using a positive tone developer). In some embodiments, the unexposed EUV area is removed by using dry development.

[0355] The dry development process can also include the use of halides, such as, for example, HCl- or HBr-based processes. Although the present disclosure is not limited to a particular theory or mechanism of operation, this approach is understood to utilize the chemical reactivity of the dry-deposited EUV photoresist film with clean chemicals (e.g., HCl, HBr, and BCl3) to form volatile products using vapor or plasma. The dry-deposited EUV photoresist film can be removed at an etching rate of up to 1 nm / s. The rapid removal of the dry-deposited EUV photoresist film by these chemical reactions is applicable to chamber cleaning, backside cleaning, bevel cleaning, and PR development. The film can be removed using vapors at various temperatures (e.g., HCl or HBr above -10°C, or BCl3 above 80°C, etc.), but the use of plasma can further promote or enhance the reactivity.

[0356] Examples of plasma processes include transformer-coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP), and devices and techniques known in the art are adopted. For example, the process may be carried out at a pressure of >0.5 mTorr (e.g., 1 - 100 mTorr), a power level of <1000 W (e.g., <500 W). The temperature is 30 - 300°C (e.g., 30 - 120°C), the flow rate is 100 - 1000 standard cubic centimeters per minute (sccm), for example, about 500 sccm, and the time may be 1 - 3000 seconds (e.g., 10 seconds - 600 seconds).

[0357] When the flow of the halide reactant is hydrogen gas and a halide gas, remote plasma / UV radiation is used to generate radicals from H2 and Cl2 and / or Br2, and the radicals of hydrogen and the halide are flowed into the reaction chamber and brought into contact with the patterned EUV photoresist on the substrate layer of the wafer. Appropriate plasma power may be in the range of 100 - 500 W without bias. These conditions are suitable for some processing reactors, such as the Kiyo etching tool available from Lam Research Corporation in Fremont, California, but it should be understood that a wider range of process conditions may be used depending on the capabilities of the processing reactor.

[0358] In the thermal development process, the substrate is exposed to a dry development chemical (e.g., a Lewis acid) in a vacuum chamber (e.g., an oven). A suitable chamber can include a vacuum line, a dry development hydrogen halide chemical gas (e.g., HBr, HCl) line, and a heater for temperature control. In some embodiments, the interior of the chamber can be coated with a corrosion-resistant film such as an organic polymer or an inorganic coating. One such coating is polytetrafluoroethylene ((PTFE), e.g., Teflon (registered trademark)). Such materials can be used in the thermal processes of the present disclosure without the risk of being removed by plasma exposure.

[0359] The process conditions for dry development depend on the photoresist film and the capping layer and their composition and properties, and the reactant flow rate can be 100 - 500 sccm (e.g., 500 sccm of HBr or HCl), the temperature can be -10 - 120 °C (e.g., -10 °C), the pressure can be 1 - 500 mTorr without plasma (e.g., 300 mTorr), and the time can be about 10 seconds to 1 minute.

[0360] In various embodiments, the methods of the present disclosure combine all dry steps of film deposition, formation by vapor deposition, (EUV) lithography photopatterning, and dry development. In such processes, the substrate may proceed directly to a dry development / etching chamber after being photopatterned in an EUV scanner. Such processes may avoid the material and production costs associated with wet development. The dry process also provides more adjustability, enabling further CD control and / or scum removal.

[0361] In various embodiments, an EUV photoresist containing some amount of metal, metal oxide, and organic components can be dry developed by heat, plasma (which may include plasma photoactivated, for example, by lamp heating or UV lamp heating), or a combination of heat and plasma methods while flowing a dry development gas containing a compound of the formula RxZy (where R = B, Al, Si, C, S, SO, x > 0, Z = Cl, H, Br, F, CH4, and y > 0). As a result of the dry development, the RxZy species can selectively remove the exposed material, leaving the unexposed portion as a mask, resulting in a positive tone. In some embodiments, the exposed portion of an organotin oxide-based photoresist film is removed by dry development in accordance with the present disclosure. Positive tone dry development may be achieved by selective dry development (removal) of the EUV exposure region, which is exposed to a flow containing hydrogen halide or hydrogen and halides (such as HCl and / or HBr) without igniting a plasma, or is exposed to a flow of H2 and Cl2 and / or Br2 using remote plasma or UV radiation generated from the plasma to generate radicals.

[0362] A wet development method can also be employed. In certain embodiments, such a wet development method is used to remove the EUV exposure area to provide a positive tone photoresist or a negative tone resist. In some embodiments, the wet development includes a neutral developer (e.g., water, a pH neutral developer) or a peroxide-containing developer (e.g., hydrogen peroxide, H2O2, etc.). Exemplary non-limiting wet development can include the use of a base in an alkaline developer (e.g., an aqueous alkaline developer). For example, ammonium such as ammonium hydroxide (NH4OH); ammonium-based ionic liquids such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), or other quaternary alkylammonium hydroxides; organic amines such as mono-, di-, and tri-organic amines (e.g., diethylamine, diethylamine, ethylenediamine, triethylenetetramine, etc.); or alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, or diethylene glycolamine, which are bases. In other embodiments, the alkaline developer can include a nitrogen-containing base. For example, a compound having the formula R N1 NH2, R N1 R N2 NH, R N1 R N2 R N3 N, or R N1 R N2 R N3 R N4 N + X N1- wherein R N1 , R N2 , R N3 , and R N4 are each independently an organic substitution component (e.g., optionally substituted alkyl or any of those described herein) or two or more organic substitution components that can be bonded together, and X N1- is OH - , F - , Cl - , Br - , I- or may contain other quaternary ammonium cation species known in the art. These bases may also contain heterocyclic nitrogen compounds known in the art, some of which are described herein. Non-limiting combinations include water and a basic developer.

[0363] Other developing methods that can be mentioned are the use of an acid in an acidic developer (e.g., an aqueous acidic developer or an acidic developer in an organic solvent) containing a halide (e.g., HCl or HBr), an organic acid (e.g., formic acid, acetic acid, or citric acid), or an organofluorine compound (e.g., trifluoroacetic acid); or the use of an organic developer such as a ketone (e.g., a ketone (e.g., 2-heptanone, cyclohexanone, or acetone), an ester (e.g., γ-butyrolactone or ethyl 3-ethoxypropionate (EEP)), an alcohol (e.g., isopropyl alcohol (IPA)), or an ether, such as a glycol ether (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA)), and combinations thereof. Non-limiting combinations include water and an acidic developer solution.

[0364] 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-heptanone, IPA, PGME, PGMEA, or combinations thereof).

[0365] Any of the developers in this specification can include one or more surfactants. The surfactant can include a positive, negative, or neutral charge and can be selected from the group consisting of fluorinated surfactants or non-fluorinated surfactants. Non-limiting examples of surfactants include quaternary ammonium salts, ammonium perfluorooctanoate salts, ammonium perfluorononanoate salts, fluorinated surfactants, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, alkylbenzene sulfonates, sodium sulfosuccinate, and sodium lauryl sulfate.

[0366] Wet development can include any useful process such as immersion development, paddle development, and spray development. After or during any of these processes, the substrate can be rotated to remove portions of the dissolved film and simultaneously dry the film.

[0367] The development process can include both wet development processes and dry development processes. Such processes can include an initial wet development followed by a subsequent dry development, or vice versa. Development can also be caused to occur in cycles, where multiple wet development processes are used, multiple dry development processes are used, or a combination of multiple wet development processes and dry development processes is employed.

[0368] Post-application process The methods in this specification can include any useful post-application process as described below.

[0369] In the backside and bevel cleaning process, by limiting the vapor and / or plasma to specific regions of the wafer, it is possible to reliably remove only the backside and bevel of the wafer without causing film degradation on the front side of the wafer. The dry-deposited EUV photoresist film being removed typically consists of Sn, O, and C, but the same cleaning approach can be extended to films of other metal oxide resists and materials. Further, this approach can also be used for film stripping and PR rework.

[0370] Process conditions suitable for dry bevel edge and backside cleaning depend on the composition and properties of the photoresist film, with reactant flow rates of 100 - 500 sccm (e.g., 500 sccm of HCl, HBr, or H2 and Cl2 or Br2, BCl3 or H2), temperature of -10 - 120 °C (e.g., 20 °C), pressure of 20 - 500 mTorr (e.g., 300 mTorr), plasma power of high frequency (e.g., 13.56 MHz) at 0 - 500 W, and time of about 10 - 20 seconds. These conditions are suitable for some processing reactors, such as the Kiyo etching tool available from Lam Research Corporation in Fremont, California, but it should be understood that a wider range of process conditions may be used depending on the capabilities of the processing reactor.

[0371] The photolithography process typically involves one or more bake steps to facilitate the chemical reactions necessary to create a chemical contrast between the exposed and unexposed areas of the photoresist. In high-volume manufacturing (HVM), such bake steps are typically performed on a track where the wafer is baked on a hot plate at a preset temperature under ambient air or, in some cases, an N2 flow. During such bake steps, by more carefully controlling the bake environment and further introducing reactive gas components into the environment, the required dosage requirements can be further reduced and / or the pattern fidelity can be improved.

[0372] According to various aspects of the present disclosure, one or more post-treatments (e.g., post-application bake (PAB)) and / or exposure (e.g., post-exposure bake (PEB)) and / or development (e.g., post-development bake (PDB)) of a deposited metal and / or metal oxide-based photoresist can increase the difference in material properties between the exposed photoresist and the unexposed photoresist, and thus, after subsequent dry development, the dose-to-size (DtS) can be reduced, the PR profile can be improved, and the line edge roughness and the width edge roughness (LER / LWR) can be improved. Such processes can involve thermal processes with control of temperature, gas atmosphere, and moisture, and as a result, the performance of dry development in subsequent processes is improved. In some examples, a remote plasma may be used.

[0373] In the case of a post-application treatment (e.g., PAB), a thermal process with control of temperature, gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, N2O, NO, Ar, He, or a mixture thereof), or under vacuum, and moisture can be used after deposition and before exposure to change the composition of the unexposed metal and / or metal oxide photoresist. This change can enhance the EUV sensitivity of the material, so that after exposure and dry development, reduction of the dose-to-size and edge roughness can be achieved.

[0374] In the case of a post-exposure treatment (e.g., isothermal holding or PEB), temperature, gas atmosphere (e.g., air, H2O, CO 2、Both the composition of the unexposed photoresist and the exposed photoresist can be changed using a thermal process in (CO, O2, O3, CH4, CH3OH, N2, H2, NH3, N2O, NO, Ar, He, or a mixture thereof), or under vacuum, with moisture control. This change can increase the difference in composition / material properties between the unexposed and exposed photoresists, and the difference in etching rates of the dry development etching gas between the unexposed and exposed photoresists. Thereby, higher etching selectivity can be achieved. Since the selectivity is improved, a more square PR profile can be obtained, the surface roughness is improved, and / or the photoresist residue / scum is reduced. In certain embodiments, the PEB can be performed in air, and optionally in the presence of moisture and CO2.

[0375] In the case of post-development processing (e.g., post-development bake or PDB), the composition of the unexposed photoresist can be changed using a thermal process in a temperature, gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, N2O, NO, Ar, He, or a mixture thereof), or under vacuum (e.g., using UV), with moisture control. In certain embodiments, the conditions also include using a plasma (e.g., including O2, O3, Ar, He, or a mixture thereof). The above change can increase the hardness of the material, which may be beneficial when using the film as a resist mask when etching the underlying substrate.

[0376] In such cases, in an alternative embodiment, the thermal process can be replaced with a remote plasma process to increase the reactive species, lower the energy barrier of the reaction, and increase productivity. Since the remote plasma can generate more reactive radicals, the reaction temperature / time of the process can be lowered, leading to an increase in productivity.

[0377] Therefore, the photoresist itself may be modified to enhance the selectivity of dry development by applying one or more processes. This thermal or radical modification can increase the contrast between the unexposed and exposed materials, thus enhancing the selectivity of subsequent dry development steps. The resulting difference in material properties between the unexposed and exposed materials can be adjusted by regulating process conditions including temperature, gas flow, moisture, pressure, and / or RF power. Dry development can provide greater process flexibility, not limited by the solubility of materials in wet developer solvents, enabling more aggressive conditions to be applied and further enhancing the achievable material contrast. The resulting high material contrast feeds back into a wider process window for dry development, enabling increased productivity, reduced costs, and improved defect performance.

[0378] A substantial limitation of wet-developed resist films is baking at limited temperatures. Since wet development depends on the solubility of materials, heating, for example, above 220 °C can cause the crosslinking degree in both the exposed and unexposed regions of metal-containing PR films to increase significantly, making both insoluble in wet developer solvents and thus preventing the film from being reliably wet-developed. For dry-developed resist films where the etching rate difference (i.e., selectivity) between the exposed and unexposed regions of the PR depends on the removal of only the exposed or unexposed portion of the resist, the processing temperature in PAB, PEB, or PDB can be varied over a much wider window to adjust and optimize the processing. For example, it is about 90 - 250 °C (e.g., 90 - 190 °C) for PAB and about 170 - 250 °C (e.g., 190 - 240 °C) for PEB and / or PDB. It has been found that the decrease in etching rate and the increase in etching selectivity occur as the processing temperature increases within the above ranges.

[0379] In certain embodiments, the PAB, PEB, and / or PDB processes may be performed with a gas ambient flow in the range of 100 to 10,000 sccm, a moisture content in an amount of several percent to up to 100% (e.g., 20 to 50%), a pressure between atmosphere and vacuum, and a duration of about 1 to 15 minutes, e.g., about 2 minutes.

[0380] Using these findings, the processing conditions may be adjusted or the process may be optimized for each specific material and situation. For example, the selectivity achieved with a given EUV dose involving a 220 - 250 °C PEB heat treatment for about 2 minutes in air with a humidity of about 20% can be made the same as that of an EUV dose about 30% higher without such heat treatment. Thus, depending on the selectivity requirements / constraints of semiconductor processing operations, the required EUV dose can be reduced using heat treatments as described herein. Alternatively, when higher selectivity is required and a higher dose is tolerated, selectivity much higher than what is possible in wet development, up to 100 times the exposure for unexposed areas, can be obtained.

[0381] Still other steps may include in - situ measurements that can evaluate physical and structural properties (e.g., critical dimension, film thickness, etc.) during the photolithography process. Modules for performing in - situ measurements include, for example, modules for light wave scattering measurement, polarization diffraction, downstream mass spectrometry, and / or plasma - excited downstream emission spectroscopy.

[0382] Figure 3A schematically shows the formation of a tin-oxo network from an alkenyl-substituted tin precursor upon reaction with water. Subsequently, upon EUV exposure of the tin-oxo network, a portion of the adjacent double bonds attached to tin are reduced, forming carbon-carbon bonds. In some embodiments, dealkylation occurs. The presence of these cross-linking hydrocarbon groups provides a hydrocarbon cross-linked secondary network, resulting in a film that is more resistant to etching, has higher sensitivity, and / or is less likely to shrink during subsequent processing steps. The hydrocarbon secondary network may, in some embodiments, be a composite film containing tin, oxygen, and carbon. In some embodiments, unsaturated groups react with the film to form, in addition to the tin-oxo network, a carbon-based secondary network, which may contain carbon that forms a cross-link between two tin centers or carbon that forms a non-volatile aliphatic chain.

[0383] Figure 3B is a reaction scheme showing the formation of a tin-halide direct bond by exposing a tin-oxo network formed from a haloaliphatic-substituted component-containing tin precursor to EUV, according to a particular disclosed embodiment. In some embodiments, dealkylation occurs. In some embodiments, the active tin centers generated during EUV exposure extract a halide from the haloaliphatic-substituted component to form an Sn-X bond, which may enhance the differentiation between the exposed and unexposed regions of the dry resist film.

[0384] Strategies to enhance the EUV sensitivity and patterning performance of isopropyl(tris)dimethylaminostannane-based dry resist processes involve incorporating carbon-fluorine (C-F) bonds into thin interfacial layers deposited directly under the resist and on amorphous carbon hard masks. The introduction of C-F moieties can be achieved using a wide range of precursor chemistries, including some commonly employed in plasma etching of silicon-based devices. Shallow incorporation of fluorine into the amorphous carbon surface can be achieved using a variety of inorganic precursors (including NF3, SF6, or F2 itself), but a useful approach to low-density C-F-rich interfacial layers involves employing hydrocarbon precursors that are partially fluorinated to a composition C n H x F y where x + y = 2n + 2. In addition to one- and two-carbon etch gases that meet the requirements, related C n H x F y compositions (where x + y = 2n) that have carbon-carbon double bonds or strained ring structures also appear to be well-suited for deposition. However, some widely used fully fluorinated precursors, such as tetrafluoroethylene or octafluorocyclobutane, give Teflon-like surfaces that are not very suitable for resist coating (at least without a co-reactant).

[0385] Figure 4A is an FTIR spectrum of a tin-oxo network formed from an alkenyl-substituted component-containing tin precursor and exposed to UV, according to a particular disclosed embodiment. As shown in the spectrum, when a film formed from a vinyltris(t-butoxy)tin precursor and water is UV-treated, the absorbance intensity of the =C-H stretching peak at 2900 - 3100 cm -1 decreases, and the absorbance of a new peak due to saturated aliphatic -C-H stretching growing at 2800 - 3000 cm -1 increases.

[0386] Figure 4B represents another Fourier transform infrared (FTIR) spectrum of a tin-oxo network formed from an alkenyl-substituted component-containing tin precursor and exposed to UV, according to a particular disclosed embodiment. In this spectrum, at 1390 cm-1 , 1250 cm -1 , 995 cm -1 , and 950 cm -1 . A decrease in the absorption of the vinyl group bending mode at was observed with UV treatment. The broad absorption in the range of 1150 - 1400 cm -1 increased with the UV treatment time. The changes observed in the IR spectrum during UV treatment are consistent with a reaction mechanism in which the alkenyl-substituted component crosslinks to the saturated alkyl network of the carbon chain and crosslinks.

[0387] Figure 4C is a scanning electron microscope (SEM) image of a tin-oxo network film formed from an alkenyl-substituted component-containing tin precursor after treatment according to a particular disclosed embodiment. The film was deposited from vinyltris(t-butoxy)tin and a water film, exposed to a scanning electron beam in the SEM, and mimicked the effects of EUV exposure followed by dry development using gaseous HBr. Dry development of the film was performed by co-flowing a mixture of 500 sccm of HBr and 500 sccm of argon at 27 °C for 120 seconds. The chamber pressure was 1 Torr. The image shows a line pattern that coincides with the electron beam scanning pattern. This line pattern could be imaged after removing the area of the film that was dry developed using HBr and not exposed to the electron beam.

[0388] Figure 5A is a table of X-ray photoelectron spectroscopy (XPS) data of a tin-oxo network film formed from a haloaliphatic-substituted component-containing tin precursor before and after treatment according to a particular disclosed embodiment. XPS analysis of the tin-oxo network film before and after heat treatment and UV radiation (to mimic EUV). The peak of tin fluoride (Sn-F bond) was observed at 688.8 eV. The peak of fluorine bonded to carbon (C-F bond) was observed at 685.6 eV. The MF / CF ratio indicates that fluorine bonded to carbon was lost and fluorine bonded to tin increased.

[0389] FIG. 5B is a scanning electron microscope (SEM) image of a tin-oxo network film formed from a haloaliphatic-substituted component-containing tin precursor after processing according to certain disclosed embodiments. For the processing of the film, after exposure to a scanning electron beam in the SEM, dry development was also performed using gaseous HBr. The film was baked at 110° C. for 2 minutes and then dry developed. The dry development of the film was carried out by co-flowing a mixture of 500 sccm of HBr and 500 sccm of Ar at 27° C. for 120 seconds. The chamber pressure was 1 Torr.

[0390] FIG. 6 is a flow diagram showing one embodiment of the process of the present invention. Process 300 for patterning a hard mask includes deposition of an underlayer. Operation 302 is optionally first depositing a diffusion barrier on the hard mask. In operation 304, the underlayer is deposited directly on the hard mask or, if a diffusion barrier layer is present, on top of it. In operation 306, a resist film is deposited on the underlayer using a tin-containing precursor. In operation 308, the resist film is exposed to extreme ultraviolet light, creating an EUV-exposed region and an EUV-unexposed region. In operation 310, an optional post-exposure bake (PEB) is performed. The pattern is then developed in operation 312.

[0391] FIG. 7 is a schematic diagram showing the structure of a tin-oxo network formed from an alkenyl-substituted component-containing tin precursor that interacts with a carbon-based underlayer in the presence of EUV when the underlayer is a carbon-based film. The carbon-based underlayer includes a mixture of saturated and unsaturated bonds and contains hydrogen, nitrogen, carbon, and / or oxygen. The carbon-based film may include unsaturated sites, which can interact with the alkenyl-substituted component from the tin precursor to promote adhesion to the underlayer of the dry resist via hydrocarbon crosslinks within the EUV-exposed region. These hydrocarbon crosslinks form a hydrocarbon secondary network, which in some embodiments can improve etch resistance and / or reduce shrinkage.

[0392] The presence of this hydrocarbon secondary network is extremely important. This is because the hydrocarbon and tin-carbon bonds in the hydrocarbon secondary network do not react with HBr during dry development. The hydrocarbon secondary network prevents HBr from accessing the tin-oxygen bonds in the metal-oxo network. In some embodiments, the hydrocarbon secondary network increases the molecular weight of the etching by-products and limits the removal of material from the EUV exposure range during dry development. The hydrocarbon secondary network thus aids in achieving the desired critical dimensions. Conventional films (those without a hydrocarbon secondary network) may shrink by about 40% to about 60% during baking and / or EUV exposure. In some embodiments, the shrinkage occurs prior to dry development and is measured after dry development has occurred. In some embodiments, the hydrocarbon secondary network may have up to a 100% increase in etch resistance compared to a film having only a metal oxo primary network. In some embodiments, the shrinkage of a resist film containing a hydrocarbon secondary network may be 20% or even lower. In some embodiments, the shrinkage of a film having a hydrocarbon secondary network may be about 5 to about 55% less than that of a resist film without a hydrocarbon secondary network. In other embodiments, the shrinkage of a film having a hydrocarbon secondary network is about 10 to about 40% less than that of a resist film without a hydrocarbon secondary network.

[0393] Figure 8 is a schematic diagram of a tin-oxo network film formed from a haloaliphatic-substituted component-containing tin precursor that interacts with a carbon-based underlayer according to certain disclosed embodiments. Upon EUV exposure, a halide is extracted from the haloaliphatic-substituted component and can directly bond to tin to form a stable, nonvolatile tin-halide bond. In some embodiments, the haloaliphatic-substituted component is a β-haloaliphatic-substituted component. For example, when the β-haloaliphatic-substituted component is -CH2-CH2-F, fluorine may be extracted during, before, or after the ethylene bond to tin is cleaved. Fluorine may then directly bond to tin in the tin-oxo network to form a nonvolatile Sn-F bond, with the concomitant release of ethylene gas.

[0394] The concept of introducing crosslinkable substitution components into the precursor can be extended to the bottom layer interface as well, such as the introduction of C-F functional groups into both the tin precursor and the active bottom layer described above. There are additional benefits and / or synergistic effects associated with implementing both, and the potential advantages are also extended to combinations with precursors such as iso-propyl(tris)dimethylaminotin in some embodiments. From amorphous / sp 3 Starting from a well-established basic process flow for depositing a rich / diamond-like ablatable hard mask (AHM) film from acetylene, a conceptually "minimal change" approach to a film exhibiting a high level of conjugated sp 2 C=C bonds may include an end step following a sharp decrease in temperature and plasma power and an increase in acetylene. However, for related compositions produced from approximate methyl-substituted acetylenes such as propylene, 1-butylene and 2-butylene, phenylacetylene or trimethylsilylacetylene, the overlap of the process space and film stability is much wider. The C-F doped bottom layer film and sp 2 Both the double bond doped bottom layer films efficiently utilize the flux of secondary electrons generated at the bottom of the tin resist / bottom layer interface, promoting the extraction of fluorine and the formation of non-volatile SnO x F y formation (in the former) and the formation of C-C and ultimately new Sn-C (bottom layer) bonds in the latter. Both mechanisms may amplify / enhance the formation of HBr etching resistant sites at the bottom film interface that counteract the effects of EUV optical depletion in some embodiments.

[0395] The presence of Sn-F bonds can increase etching resistance and / or reduce shrinkage.

[0396] Device The present disclosure also includes any apparatus configured to perform any of the methods described herein. In one embodiment, an apparatus for depositing a film includes a deposition module that includes a chamber for depositing an EUV-sensitive material as a film by providing a metal-containing precursor in the presence of an optional ligand-containing precursor, a patterning module that includes an EUV lithography tool having a radiation source with a wavelength of less than 30 nm, and a development module that includes a chamber for developing the film.

[0397] The apparatus can further include a controller having instructions for such modules. In one embodiment, the controller includes one or more memory devices, one or more processors, and system control software encoded with instructions for performing the deposition of a film or a capping layer. Such modules can include, for example, in the deposition module, depositing a resist film on the upper surface of a substrate or on a photoresist layer, in the patterning module, forming a pattern in the film by directly patterning the film with a resolution of less than 30 nm by EUV exposure, and in the development module, developing the film. In certain embodiments, the development module removes the EUV-exposed area or the non-EUV-exposed area, thereby providing a pattern in the film.

[0398] FIG. 9 is a schematic view of an embodiment of a process station 400 having a process chamber body 402 for maintaining a low-pressure environment suitable for performing the dry stripping and development described. A plurality of process stations 400 may be included in a common low-pressure process tool environment. For example, FIG. 10 shows an embodiment of a multi-station processing tool 500 such as a VECTOR® processing tool available from Lam Research Corporation of Fremont, Calif. In some embodiments, one or more hardware parameters of the process station 400, including those discussed in detail below, may be programmatically adjusted by one or more computer controllers 450.

[0399] The process station may be configured as a module within a cluster tool. FIG. 12 shows a semiconductor process cluster tool architecture having a vacuum integration deposition module and a patterning module suitable for implementation of the embodiments described herein. Such a cluster process tool architecture can include modules for resist deposition, resist exposure (EUV scanner), resist dry development, and etching, as described herein with reference to FIGS. 11 and 12.

[0400] In some embodiments, certain of the processing functions, such as for example dry development and etching, can be carried out sequentially within the same module. And the methods and apparatuses of the embodiments of the present disclosure are for receiving a wafer, such as a photo-patterned EUV resist thin film layer disposed on an etching target layer or layer stack, into a dry development / etching chamber after photo-patterning in an EUV scanner, dry developing the photo-patterned EUV resist thin film layer, and then etching an underlying layer using the patterned EUV resist as a mask as described herein.

[0401] Returning to FIG. 9, the process station 400 is in fluid communication with a reactant delivery system 401 for sending a process gas to a distribution showerhead 406 via a connection 405. The reactant delivery system 401 optionally includes a mixing vessel 404 for blending and / or conditioning the process gas for sending to the showerhead 406. The introduction of the process gas into the mixing vessel 404 may be controlled by one or more mixing vessel inlet valves 420. When using plasma exposure, the plasma may be sent to the showerhead 406 or generated within the process station 400. The process gas can include any of those described herein, such as for example a metal-containing precursor, a ligand-containing precursor, or a counter-reactant.

[0402] Figure 9 includes an optional vaporization point 403 for vaporizing the liquid reactant supplied to the mixing vessel 404. The liquid reactant can include a metal-containing precursor, a ligand-containing precursor, or a counter-reactant. In some embodiments, a liquid flow controller (LFC) upstream of the vaporization point 403 may be provided to control the mass flow rate of the liquid for vaporization and delivery to the process station 400. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. The plunger valve of the LFC may then be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller that is in electrical communication with the MFM.

[0403] The showerhead 406 distributes the process gas toward the substrate 412. In the embodiment shown in Figure 9, the substrate 412 is located below the showerhead 406 and is illustrated as being placed on the pedestal 408. The showerhead 406 may have any suitable shape and may have any suitable number and arrangement of ports for distributing the process gas to the substrate 412.

[0404] In some embodiments, the pedestal 408 may be raised or lowered to expose the substrate 412 in the volume portion 407 between the substrate 412 and the showerhead 406. It will be understood that in some embodiments, the height of the pedestal may be programmatically adjusted by a suitable computer controller 450.

[0405] In some embodiments, the pedestal 408 may be temperature-controlled via the heater 410. In some embodiments, the pedestal 408 may be heated to a temperature above 0°C and up to a maximum of 300°C or more, such as 50 - 120°C (such as about 65 - 80°C, etc.) during non-plasma thermal exposure to dry developing chemicals such as HBr, HCl, or BCl3 of the photopatterned resist as described in the disclosed embodiments.

[0406] Furthermore, in some embodiments, the pressure control of the process station 400 may be provided by the butterfly valve 418. As shown in the embodiment of FIG. 9, the butterfly valve 418 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, the pressure control of the process station 400 may be adjusted by changing the flow rate of one or more gases introduced into the process station 400.

[0407] In some embodiments, the position of the showerhead 406 may be adjusted relative to the pedestal 408 to vary the volume portion 407 between the substrate 412 and the showerhead 406. Furthermore, it will be understood that the vertical position of the pedestal 408 and / or the showerhead 406 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 408 may include a rotation axis for rotating the orientation of the substrate 412. It will be understood that one or more of these adjustment examples may be programmatically implemented by one or more suitable computer controllers 450.

[0408] When plasma can be used, for example, in gentle plasma-based dry development embodiments and / or in etching operations performed within the same chamber, the showerhead 406 and the pedestal 408 are in electrical communication with a radio frequency (RF) power source 414 and a matching network 416 for powering the plasma. In some embodiments, the plasma energy may be controlled by controlling one or more of the process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power source 414 and the matching network 416 may be operated at any suitable power to form a plasma having radical species of a desired composition. An example of a suitable power is up to about 500 W.

[0409] In some embodiments, the instructions to the controller 450 may be provided through input / output control (IOC) sequence instructions. In one example, the instructions for setting the conditions of a process step may be included in the corresponding recipe step of a process recipe. In some cases, the process recipe steps may be arranged in sequence such that all the instructions for a process step are executed simultaneously with that process step. In some embodiments, the instructions for setting one or more reactor parameters may be included in a recipe step. For example, a recipe step may include instructions for setting the flow rate of a dry development chemical reaction inert gas such as HBr or HCl, and a time delay instruction for that recipe step. In some embodiments, the controller 450 may include any of the features related to the system controller 550 of FIG. 10 described below.

[0410] As described above, one or more process stations may be included in the multi-station processing tool. FIG. 10 is a schematic diagram of one embodiment of a multi-station processing tool 500 having an inbound load lock 502 and an outbound load lock 504, where one or both may include a remote plasma source. Robot 506 is configured to move wafers from a cassette loaded through pod 508 at atmospheric pressure through atmospheric port 510 to inbound load lock 502. The wafer is placed on pedestal 512 within inbound load lock 502 by robot 506, atmospheric port 510 is closed, and the load lock is pumped down. If inbound load lock 502 includes a remote plasma source, the wafer may be exposed to remote plasma processing within the load lock to treat the silicon nitride surface prior to being introduced into process chamber 514. Further, the wafer may also be heated within inbound load lock 502, for example, to remove moisture and adsorbed gases. Next, chamber transfer port 516 to process chamber 514 is opened, and another robot (not shown) places the wafer on the pedestal of the illustrated first station within the reactor for processing. The embodiment shown in FIG. 10 includes load locks, but it will be understood that in some embodiments, the wafer may be placed directly into the process station.

[0411] The illustrated processing chamber 514 includes four processing stations numbered 1-4 in the embodiment shown in FIG. 10. Each station has a heated pedestal (shown as 518 for station 1) and a gas line inlet. It will be appreciated that each process station may have different or multiple purposes in some embodiments. For example, in some embodiments, the process station may be switchable between a dry development mode and an etching process mode. Additionally, or alternatively, in some embodiments, the processing chamber 514 may include one or more matching pairs of a dry development station and an etching process station. Although the illustrated processing chamber 514 includes four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, the processing chamber may have five or more stations, while in other embodiments, the processing chamber may have three or fewer stations.

[0412] FIG. 10 shows one embodiment of a wafer handling system 590 for transporting wafers within the processing chamber 514. In some embodiments, the wafer handling system 590 may transport wafers between various process stations and / or between a process station and a load lock. It will be understood that any suitable wafer handling system may be employed. Non-limiting examples include a wafer carousel and a wafer handling robot. FIG. 10 also shows an embodiment of a system controller 550 employed to control the process conditions and hardware state of the process tool 500. The system controller 550 may include one or more memory devices 556, one or more mass storage devices 554, and one or more processors 552. The processor 552 may include a CPU or computer, analog and / or digital input / output connections, a stepping motor controller board, etc.

[0413] In some embodiments, system controller 550 controls all of the activities of process tool 500. System controller 550 executes system control software 558 that is stored in mass storage device 554, loaded into memory device 556, and executed on processor 552. Alternatively, control logic may be hard-coded into controller 550. For these purposes, application specific integrated circuits, programmable logic devices (e.g., field programmable gate arrays, i.e., FPGAs), etc. may be used. In the following discussion, when “software” or “code” is used, functionally comparable hard-coded logic may be used instead. System control software 558 may include instructions for controlling timing, gas mixing, gas flow rate, pressure of the chamber and / or station, temperature of the chamber and / or station, wafer temperature, target power level, RF power level, position of the substrate pedestal, chuck and / or susceptor, and other parameters of the particular process implemented by process tool 500. System control software 558 may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be described to control the operation of process tool components used to execute various process tool processes. System control software 558 may be coded in any suitable computer readable programming language.

[0414] In some embodiments, the system controller software 558 may include input / output control (IOC) sequence instructions for controlling the various parameters described above. Other computer software and / or programs stored in the mass storage device 554 and / or the memory device 556 associated with the system controller 550 may be employed in some embodiments. Examples of programs or portions of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0415] The substrate positioning program may include program code for a process tool component that mounts a substrate on the pedestal 518 and controls the spacing between the substrate and other parts of the process tool 500.

[0416] The process gas control program may include code for controlling various gas compositions (e.g., HBr or HCl gas as described herein) and flow rates, and optionally for flowing gas into one or more process stations prior to deposition to stabilize the pressure within the process station. The pressure control program may include code for controlling the pressure within the process station, for example, by regulating the throttle valve of the exhaust system of the process station, the gas flow to the process station, etc.

[0417] The heater control program may include code for controlling the current to a heating unit used to heat the substrate. Alternatively, the heater control program may control the delivery of a heat transfer gas (such as helium) to the substrate.

[0418] The plasma control program may include code for setting the RF power level applied to the process electrodes of one or more process stations in accordance with the embodiments herein.

[0419] The pressure control program may include code for maintaining the pressure within the reaction chamber in accordance with the embodiments of this specification.

[0420] In some embodiments, there may be a user interface associated with the system controller 550. The user interface may include a display screen, a graphical software display of the device and / or process conditions, and user input devices such as a pointing device, a keyboard, a touch screen, a microphone, etc.

[0421] In some embodiments, the parameters adjusted by the system controller 550 may be related to the process conditions. Non-limiting examples include the composition and flow rate of the process gas, temperature, pressure, plasma conditions (e.g., RF bias power level), etc. These parameters may be provided to the user in the form of a recipe, and the recipe may be input using the user interface.

[0422] Signals for monitoring the process may be provided by the analog and / or digital input connections of the system controller 550 from various process tool sensors. Signals for controlling the process may be output on the analog and digital output connections of the process tool 500. Non-limiting examples of process tool sensors that can be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriate programmed feedback and control algorithms may be used with the data from these sensors to maintain the process conditions.

[0423] The system controller 550 may provide program instructions for carrying out the deposition process described above. The program instructions may control various process parameters such as DC power level, RF bias power level, pressure, temperature, etc. The instructions may control parameters for operating the dry development process and / or the etching process according to the various embodiments described herein.

[0424] The system controller 550 typically includes one or more memory devices and one or more processors configured to execute instructions so that the apparatus performs the methods according to the disclosed embodiments. A machine-readable medium including instructions for controlling process operations according to the disclosed embodiments may be coupled to the system controller 550.

[0425] In some examples, the system controller 550 may be part of a system that may also be part of the examples described above. Such a system may include semiconductor processing equipment such as one or more processing tools, one or more chambers, one or more processing platforms, and / or certain processing components (such as wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling the operation of the system before, during, and after processing of a semiconductor wafer or substrate. This electronics may be referred to as a "controller" that can control various components or sub-components of the system(s). The system controller 550 may be programmed to control any of the processes such as delivery of process gases, temperature setting (e.g., heating and / or cooling), pressure setting, vacuum setting, power setting, radio frequency (RF) generator setting, RF matching circuit setting, frequency setting, flow rate setting, fluid delivery setting, position and motion setting, loading and unloading of wafers to and from the tool, and loading and unloading of wafers to and from other transfer tools and / or load locks connected or interfaced to a particular system, depending on the processing conditions and / or the type of system, as disclosed herein.

[0426] Broadly speaking, system controller 550 may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that, for example, receive commands, issue commands, control operations, enable cleaning operations, enable endpoint measurement, etc. The integrated circuits may include chips in the form of firmware that stores program instructions, digital signal processors (DSPs), chips defined as application-specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (such as software). The program instructions are instructions transmitted to the system controller 550 in the form of various individual settings (or program files), and may define operating parameters for performing a specific process on a semiconductor wafer or for the semiconductor wafer, or on the system. The operating parameters may, in some embodiments, be part of a recipe defined by a process engineer to achieve one or more processing steps in the manufacture of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or types of wafers.

[0427] The system controller 550 may, in some embodiments, be part of a computer integrated with the system, coupled to the system, or otherwise network-connected to the system, or may be coupled to such a computer, or a combination thereof. For example, the system controller 550 may be all or part of a host computer system within the "cloud" or in a manufacturing plant that enables remote access to wafer processing. This computer can monitor the current progress of manufacturing operations, verify the history of past manufacturing operations, and verify trends or performance criteria from multiple manufacturing operations to change the parameters of the current process, set the processing steps following the current process, or start a new process by enabling remote access to the system. In some examples, a remote computer (e.g., a server) can provide a process recipe to the system through a network that may include a local network or the Internet. The remote computer may include a user interface that enables the input or programming of parameters and / or settings, and the parameters and / or settings are then transmitted from the remote computer to the system. In some examples, the system controller 550 receives instructions in a data format that defines the parameters of each processing step performed during one or more operations. It should be understood that this parameter may be specific to the type of process being performed and the type of tool that the system controller 550 is configured to interface with or control. Thus, as described above, the system controller 550 may be distributed, such as by including one or more separate controllers network-connected to each other and working towards a common purpose such as the processes and controls described herein. Examples of controllers distributed for such a purpose include one or more integrated circuits on a chamber that are combined to communicate with one or more integrated circuits remotely located (e.g., at the platform level or as part of a remote computer) for controlling the process on the chamber.

[0428] Although not limited, exemplary systems may include a plasma etching chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etching chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an atomic layer etching (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, an EUV lithography chamber (scanner) or module, a dry deposition chamber or module, and any other semiconductor processing system that may be associated with or used in the manufacture and / or production of semiconductor wafers.

[0429] As described above, depending on one or more process steps performed by a tool, system controller 550 may communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout the factory, main computers, other controllers, or tools used for material transport that load and unload wafer containers at tool positions and / or load ports within a semiconductor manufacturing facility.

[0430] In certain embodiments, an inductively coupled plasma (ICP) reactor suitable for etching operations suitable for implementation in some embodiments is described herein. Although the ICP reactor is described herein, it should be understood that capacitively coupled plasma reactors may be used in some embodiments.

[0431] FIG. 11 schematically shows a cross-sectional view of an inductively coupled plasma apparatus 600 suitable for implementing certain embodiments or aspects of embodiments such as dry development and / or etching. One example thereof is the Kiyo (registered trademark) reactor manufactured by Lam Research Corporation of Fremont, California. In other embodiments, it may be implemented using other tools or tool types having the function of performing the dry development and / or etching processes described herein.

[0432] The inductively coupled plasma apparatus 600 includes an overall process chamber structurally defined by a chamber wall 601 and a window 611. The chamber wall 601 can be manufactured from stainless steel or aluminum. The window 611 can be manufactured from quartz or other dielectric materials. An optional internal plasma grid 650 divides the overall process chamber into an upper sub-chamber 602 and a lower sub-chamber 603. In most embodiments, the plasma grid 650 may be removed, thereby enabling utilization of the chamber space formed from sub-chambers 602 and 603. A chuck 617 is located near the bottom inner surface within the lower sub-chamber 603. The chuck 617 is configured to receive and hold a semiconductor wafer 619 on which etching and deposition processes are performed. The chuck 617 can be an electrostatic chuck for supporting the wafer 619 when the wafer 619 is present. In some embodiments, an edge ring (not shown) surrounds the chuck 617 and has an upper surface that is substantially coplanar with the upper surface of the wafer 619 when present above the chuck 617. The chuck 617 also includes electrostatic electrodes for chucking and de-chucking the wafer 619. A filter and a DC clamp power supply (not shown) may be provided for this purpose.

[0433] Other control systems can also be provided for lifting the wafer 619 from the chuck 617. The chuck 617 can be electrically charged using the RF power supply 623. The RF power supply 623 is connected to the matching circuit 621 through the connection portion 627. The matching circuit 621 is connected to the chuck 617 through the connection portion 625. In this way, the RF power supply 623 is connected to the chuck 617. In various embodiments, the bias power of the electrostatic chuck may be set to about 50V, or may be set to different bias powers according to the process implemented according to the disclosed embodiments. For example, the bias power may be about 20V to about 100V, or about 30V to about 150V.

[0434] Elements for plasma generation include coil 633 located above window 611. In some embodiments, no coil is used in the disclosed embodiments. Coil 633 is manufactured from an electrically conductive material and includes at least one complete winding. In the example of coil 633 shown in FIG. 11, it includes three windings. The cross-section of coil 633 is indicated by symbols, where the "X" coil rotates into the page and extends, and the "●" coil rotates out of the page and extends. Elements for plasma generation also include RF power supply 641 configured to supply RF power to coil 633. Typically, RF power source 641 is connected to matching circuit 639 through connection 645. Matching circuit 639 is connected to coil 633 through connection 643. In this way, RF power source 641 is connected to coil 633. Optional Faraday shield 649 is located between coil 633 and window 611. Faraday shield 649 may be maintained in a spaced relationship with respect to coil 633. In some embodiments, Faraday shield 649 is disposed directly above window 611. In some embodiments, the Faraday shield is between window 611 and chuck 617. In some embodiments, the Faraday shield is not maintained in a spaced relationship with respect to coil 633. For example, the Faraday shield may be flush directly below the window. Coil 633, Faraday shield 649, and window 611 are each configured to be substantially parallel to each other. Faraday shield 649 may prevent metal or other species from depositing on window 611 of the process chamber.

[0435] Process gas may flow into the process chamber through one or more gas flow main inlets 660 located in the upper sub-chamber 602 and / or through one or more gas flow side inlets 670. Similarly, although not explicitly shown, similar gas flow inlets may be used to supply process gas to the capacitively coupled plasma processing chamber. A vacuum pump, such as a single- or two-stage mechanical dry pump and / or a turbomolecular pump 640, may be used to draw process gas out of the process chamber and maintain the pressure within the process chamber. For example, a vacuum pump may be used to evacuate the lower sub-chamber 603 during the purge operation of ALD. A valve-controlled conduit may be used to fluidly connect the vacuum pump to the process chamber so that the application of the vacuum environment provided by the vacuum pump can be selectively controlled. This may be done by employing a closed-loop control flow restriction device, such as a throttle valve (not shown) or a pendulum valve (not shown), during the operation of the plasma process. Similarly, a fluid connection section that controls the vacuum pump and the valve to the capacitively coupled plasma processing chamber may also be employed.

[0436] During operation of the apparatus 600, one or more process gases may be supplied through the gas flow inlets 660 and / or 670. In certain embodiments, the process gas may be supplied only through the gas flow main inlet 660 or only through the gas flow side inlet 670. In some cases, each of the illustrated gas flow inlets may be replaced with a more complex gas flow inlet, such as one or more showerheads. The Faraday shield 649 and / or the optional grid 650 may include internal channels and holes that allow the process gas to be sent to the process chamber. Either or both of the Faraday shield 649 and the optional grid 650 may function as a showerhead for sending the process gas. In some embodiments, by placing a liquid vaporization and delivery system upstream of the process chamber, when a liquid reactant or precursor is vaporized, the vaporized reactant or precursor may be introduced into the process chamber through the gas flow inlets 660 and / or 670.

[0437] Radio frequency power is supplied from the RF power supply 641 to the coil 633, and an RF current flows through the coil 633. The RF current flowing through the coil 633 generates an electromagnetic field. The electromagnetic field generates an induced current in the upper sub-chamber 602. Through the physical and chemical interactions between the generated various ions and radicals and the wafer 619, features are etched and layers are selectively deposited on the wafer 619.

[0438] When the plasma grid 650 is used such that both the upper sub-chamber 602 and the lower sub-chamber 603 are present, the induced current acts on the gas present in the upper sub-chamber 602 to generate an electron-ion plasma in the upper sub-chamber 602. The optional internal plasma grid 650 limits the amount of hot electrons in the lower sub-chamber 603. In some embodiments, the apparatus 600 is designed and operated such that the plasma present in the lower sub-chamber 603 is an ion-ion plasma.

[0439] Both the upper electron-ion plasma and the lower ion-ion plasma may contain positive ions and negative ions, but in the ion-ion plasma, the ratio of negative ions to positive ions is larger. Volatile etching and / or deposition by-products may be removed from the lower sub-chamber 603 through the port 622. The chuck 617 disclosed herein may operate at an elevated temperature in the range of about 10 to 250 °C. The temperature will depend on the process operation and the particular recipe.

[0440] The apparatus 600 may be connected to a facility (not shown) when installed in a clean room or a manufacturing facility. The facility includes piping that provides process gas, vacuum, temperature control, and control of environmental particles. These facilities are connected to the apparatus 600 when installed in the target manufacturing facility. Further, the apparatus 600 may be connected to a transfer chamber that allows for the loading and unloading of semiconductor wafers into and out of the apparatus 600 by robotics using typical automation.

[0441] In some embodiments, system controller 630 (which may include one or more physical or logical controllers) controls some or all of the operations of the process chamber. The system controller 630 may include one or more memory devices and one or more processors. In some embodiments, apparatus 600 includes a switching system for controlling flow rate and duration when the disclosed embodiments are implemented. In some embodiments, apparatus 600 may have a switching time of up to about 600 ms, or up to about 750 ms. The switching time may depend on the flow chemistry reaction, the selected recipe, the reactor architecture, and other factors.

[0442] In some examples, system controller 630 may be part of a system that may also be part of the examples described above. Such a system can include semiconductor processing equipment such as one or more processing tools, one or more chambers, one or more processing platforms, and / or certain processing components (such as wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling the operation of the system before, during, and after the processing of a semiconductor wafer or substrate. This electronics may be incorporated into system controller 630 that can control various components or sub-components of the system(s). The system controller may be programmed to control any of the processes disclosed herein, such as delivery of process gases, temperature setting (e.g., heating and / or cooling), pressure setting, vacuum setting, power setting, radio frequency (RF) generator setting, RF matching circuit setting, frequency setting, flow rate setting, fluid delivery setting, position and motion setting, loading and unloading of wafers to and from the tool, and loading and unloading of wafers to and from other transfer tools and / or load locks that are connected or coordinated with a particular system, depending on the processing parameters and / or the type of system.

[0443] Broadly speaking, the system controller 630 may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that, for example, receive commands, issue commands, control operations, enable cleaning operations, enable endpoint measurement, and the like. The integrated circuits may include chips in the form of firmware that stores program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). The program instructions are instructions transmitted to the controller in the form of various individual settings (or program files) that may define operating parameters for performing a particular process on a semiconductor wafer or for a semiconductor wafer or for the system. The operating parameters may, in some embodiments, be part of a recipe defined by a process engineer to achieve one or more processing steps in the manufacture or removal of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer types.

[0444] In some embodiments, system controller 630 may be part of a computer integrated with the system, coupled to the system, or otherwise network-connected to the system, or may be coupled to such a computer, or may be a combination thereof. For example, the controller may be within the "cloud" or all or part of a host computer system in a manufacturing facility that enables remote access to wafer processing. This computer may monitor the current progress of manufacturing operations, verify the history of past manufacturing operations, and verify trends or performance criteria from multiple manufacturing operations to change the parameters of the current process, set the process steps following the current process, or initiate a new process by enabling remote access to the system. In some examples, a remote computer (e.g., a server) may provide a process recipe to the system through a network that may include a local network or the Internet. The remote computer may include a user interface that enables input or programming of parameters and / or settings, and the parameters and / or settings are then transmitted from the remote computer to the system. In some examples, system controller 630 receives instructions in a data format that defines the parameters of each process step performed during one or more operations. It should be understood that this parameter may be specific to the type of process being performed and the type of tool that the controller is configured to interface with or control. Thus, as described above, system controller 630 may be distributed by including one or more separate controllers network-connected to each other and working towards a common purpose such as the processes and controls described herein. Examples of controllers distributed for such a purpose include one or more integrated circuits on a chamber that are combined to communicate with one or more integrated circuits remotely located (e.g., at the platform level or as part of a remote computer) to control the process on the chamber.

[0445] Although not limited, exemplary systems may include a plasma etching chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etching chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an ALE chamber or module, an ion implantation chamber or module, a track chamber or module, an EUV lithography chamber (scanner) or module, a dry deposition chamber or module, and any other semiconductor processing system that may be associated with or used in the manufacture and / or production of semiconductor wafers.

[0446] As described above, depending on one or more process steps performed by a tool, the controller may communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools installed throughout the factory, a main computer, other controllers, or tools used for material transport to and from a wafer container at a tool location and / or load port within a semiconductor manufacturing facility.

[0447] EUVL patterning may be performed using a suitable tool (often referred to as a scanner), such as the TWINSCAN® NXE:3300B platform provided by ASML in Veldhoven, the Netherlands, etc. The EUVL patterning tool may be a stand-alone device where substrates are loaded and unloaded for deposition and etching, as described herein. Alternatively, as described below, the EUVL patterning tool may be a module on a larger multi-component tool. FIG. 12 shows a semiconductor process cluster tool architecture having a vacuum integrated deposition module interfaced with a vacuum transfer module, an EUV patterning module, and a dry development / etching module, suitable for implementing the processes described herein. The process may be carried out without such a vacuum integrated device, but such a device is advantageous in some embodiments.

[0448] FIG. 12 shows a semiconductor process cluster tool architecture 700 having a vacuum integrated deposition module interfaced with a vacuum transfer module and a patterning module, suitable for implementing the processes described herein. The arrangement of transfer modules for "transferring" wafers between a plurality of storage facilities and processing modules may be referred to as a "cluster tool architecture" system. The deposition module and the patterning module are vacuum integrated according to the requirements of a specific process. Other modules for etching, etc. may also be included in the cluster.

[0449] The vacuum transfer module (VTM) 738 interfaces with four processing modules 720a - 720d, which may be individually optimized to perform various manufacturing processes. As an example, the processing modules 720a - 720d may be implemented to perform deposition, evaporation, ELD, dry development, etching, strip, and / or other semiconductor processes. For example, module 720a may be an ALD reactor operable to perform non - plasma thermal atomic layer deposition as described herein, such as a Vector tool available from Lam Research Corporation of Fremont, California, etc. Module 720b may be a PECVD tool such as Lam Vector®. It should be understood that the figures are not necessarily drawn to scale.

[0450] Airlocks 742 and 746, also known as load locks or transfer modules, interface with the VTM 738 and the patterning module 740. For example, as described above, a suitable patterning module is the TWINSCAN® NXE:3300B platform provided by ASML of Veldhoven, the Netherlands. This tool architecture enables a workpiece such as a semiconductor substrate or wafer to be transferred under vacuum so as not to react prior to exposure. The integration of the deposition module with the lithography tool is driven by the fact that EUVL also requires a significant vacuum due to the strong light absorption of incident photons by ambient gases such as H2O, O2, etc.

[0451] As described above, this integrated architecture is only one possible embodiment of the tools for implementing the described process. Also, this process can be implemented by integrating a more conventional stand-alone EUVL scanner and a deposition reactor such as a Lam Vector tool, either stand-alone or, for example, as modules that do not include an integrated patterning module, with other tools such as etching, strip, etc. (e.g., Lam's Kiyo tool or Gamma tool) within a cluster architecture, as described with reference to FIG. 12.

[0452] Airlock 742 may be an "outgoing" load lock (i.e., referring to the transfer of the substrate from VTM 738 serving deposition module 720a to patterning module 740), and airlock 746 may be an "incoming" load lock (i.e., meaning the transfer of the substrate back from patterning module 740 to VTM 738). The incoming load lock 746 may also provide an interface with the outside of the tool for the entry and exit of substrates. Each process module has a face that interfaces with VTM 738. For example, deposition process module 720a has face 736. Inside each face, sensors, such as sensors 1 - 18 as illustrated, are used to detect the passage of wafer 726 as it moves between each station. The patterning module 740 and airlocks 742 and 746 may similarly be provided with additional faces and sensors (not shown).

[0453] The main VTM robot 722 transports the wafer 726 between modules including airlocks 742 and 746. In one embodiment, the robot 722 has one arm, and in another embodiment, the robot 722 has two arms, and each arm has an end effector 724 for picking up wafers such as the wafer 726 for transportation. The front-end robot 744 is used to transport the wafer 726 from the outfeed airlock 742 into the patterning module 740 and from the patterning module 740 into the infeed airlock 746. The front-end robot 744 can also transport the wafer 726 between the infeed load lock and the outside of the tool for the entry and exit of the substrate. Since the infeed airlock module 746 has the ability to match the environment between the atmosphere and the vacuum, the wafer 726 can move between the two pressure environments without being damaged.

[0454] Note that EUVL tools typically operate at a higher vacuum than deposition tools. In such cases, it is desirable to increase the vacuum environment of the substrate during transportation to the EUVL tool between depositions and to be able to degas the substrate before entering the patterning tool. The provision of this function by the outfeed airlock 742 can be done by holding the transported wafer at a lower pressure, not higher than the pressure in the patterning module 740, for a certain period of time to discharge off-gas so that the optical system of the patterning tool 740 is not contaminated by the gas discharged from the substrate. A pressure suitable for the gas-discharging outfeed airlock is only 1E-8 Torr.

[0455] In some embodiments, a system controller 750 (which may include one or more physical or logical controllers) controls some or all of the operation of the cluster tool and / or its individual modules. Note that the controller may be local to the cluster architecture, or may be located externally to the cluster architecture on the manufacturing floor, or may be located at a remote location and connected to the cluster architecture via a network. The system controller 750 may include one or more memory devices and one or more processors. The processor may include components such as a central processing unit (CPU) or computer, analog and / or digital input / output connections, and a stepper motor controller board. Instructions for performing appropriate control operations are executed on the processor. These instructions may be stored in a memory device associated with the controller or may be provided via a network. In certain embodiments, the system controller executes system control software.

[0456] The system control software may include instructions for controlling the timing and / or magnitude of the application of any aspect of the tool or module operation. The system control software may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be described to control the operation of the process tool components required to perform various tool processes. The system control software may be coded in any suitable computer-readable programming language. In some embodiments, the system control software includes input / output control (IOC) sequence instructions for controlling the various parameters described above. For example, each stage of a semiconductor manufacturing process may include one or more instructions for execution by the system controller. Instructions for setting process conditions for condensation, deposition, evaporation, patterning, and / or etching stages may be included, for example, in the corresponding recipe stage.

[0457] In various embodiments, an apparatus for forming a negative-type pattern mask is provided. The apparatus may include a processing chamber for patterning, deposition, and etching, and a controller including instructions for forming a negative-type pattern mask. The instructions may include code for patterning features of a chemically amplified (CAR) resist on a semiconductor substrate by EUV exposure to expose the surface of the substrate, dry-developing the photopatterned resist, and etching an underlying layer or layer stack using the patterned resist as a mask within the processing chamber.

[0458] Note that the computer controlling the movement of the wafer can be local to the cluster architecture, or can be located externally to the cluster architecture of the manufacturing floor, or can be located at a remote location and connected to the cluster architecture via a network.

[0459] Conclusion The foregoing embodiments have been described in some detail for purposes of clarity of understanding, but it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. The embodiments disclosed herein may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the disclosed embodiments. Further, the disclosed embodiments are described in conjunction with specific embodiments, but it will be understood that the specific embodiments are not intended to limit the disclosed embodiments. It should be noted that there are many alternative ways to implement the processes, systems, and apparatuses of this embodiment. Accordingly, this embodiment is considered to be illustrative and not restrictive, and this embodiment is not limited to the details shown herein.

Claims

1. A precursor composition for forming a radiation-sensitive resist film, wherein the precursor composition comprises Formula M(R 1 ) 4 wherein M is a metal selected from the group consisting of lead, germanium, tin, and hafnium; and R 1 are each independently an aliphatic, alkylsilyl, amino, amido, azido, cyano, alkylcarbonyl, isocyanato, isothiocyanato, thiocyanato, alkoxy, heterocyclyl, aryl, alkenyl, or alkynyl, or R 1 The substituent moieties may be linked to form a ring, and at least one R 1 is an unsaturated substituted moiety; after the precursor is deposited on a substrate, it forms a metal-oxo network primary film having an unsaturated substitution component, When the unsaturated substitution component in the metal-oxo network primary film is exposed to radiation, when M is tin and R 1 are the same respectively, a hydrocarbon secondary network is formed under the condition that R 1 is alkynyl. A precursor composition.

2. The precursor composition according to claim 1, The precursor composition, wherein the hydrocarbon secondary network increases the etching resistance.

3. The precursor composition according to claim 1, The precursor composition, wherein the hydrocarbon secondary network reduces the film shrinkage after patterning.

4. The precursor composition according to claim 1, M is tin, and two aliphatic Rs 1 A precursor composition containing less than 0.5% of a tin-containing compound containing a substitution component.

5. A method for processing a semiconductor substrate, the method comprising The precursor of formula M(R 1 ), wherein M is a metal selected from the group consisting of lead, germanium, tin, and hafnium, and R 4 are each independently aliphatic, alkylsilyl, amino, amide, azide, cyano, alkylcarbonyl, isocyanato, isothiocyanato, thiocyanato, alkoxy, heterocyclyl, aryl, alkenyl, or alkynyl, or the R 1 substitution components may be linked to form a ring, and at least one R 1 is an unsaturated substitution component. The precursor is deposited on a substrate under the condition that M is tin and R 1 is alkynyl when they are the same, to form an irradiation-sensitive metal-oxo network resist film, and 1 when they are the same, R 1 is alkynyl. forming a photopatterned metal-oxo network resist film by patterning the metal-oxo network resist film having an unsaturated substitution component by extreme ultraviolet exposure, A method of forming a photopatterned and crosslinked metal-oxo network resist film by forming a hydrocarbon secondary network when the unsaturated substitution component in the metal-oxo network resist film is exposed to radiation.

6. The method according to claim 5, The method further comprising forming a resist mask by dry-developing the photopatterned and crosslinked metal-oxo network resist film.

7. The method according to claim 5, The method, wherein the hydrocarbon secondary network increases the etching resistance.

8. The method according to claim 5, The method, wherein the hydrocarbon secondary network reduces the film shrinkage after patterning.

9. The method according to claim 5, The method, wherein the metal is tin.

10. The method according to claim 9, The precursor comprises the structure of formula (I), 【Chemical Formula 9】 In the formula, R 2 is C 2-6 is aliphatic, L is independently NR 3 R 4 or OR 5 and R 3 R 4 and R 5 are each independently hydrogen, alkylcarbonyl, or aliphatic, and R 3 substituent and R 4 substituents may be linked to form a ring Method.

11. The method according to claim 10, L is NR respectively 3 R 4 The method is as follows

12. The method according to claim 11, The method, wherein L is dimethylamino, tert-butylamino, diethylamino, ethylmethylamino, methylpropylamino, pyrrolidino, or piperidino.

13. The method according to claim 10, L is OR respectively 5 which is a method

14. The method according to claim 13, The method, wherein L is methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, or n-butoxy.

15. The method according to claim 5, wherein wherein the unsaturated substitution component is C 2 -C 6 alkenyl, C 2 -C 6 branched alkenyl, or C 2 -C 6 alkynyl, method.

16. The method according to claim 5, wherein wherein the unsaturated substitution component is C 5 -C 6 -alkenyl, C 5 -C 6 -branched alkenyl, or C 5 -C 6 -alkynyl, method.

17. The method according to claim 9, wherein the precursor is vinyltri(methoxy)tin, vinyltri(ethoxy)tin, vinyltri(isopropoxy)tin, vinyltri(tert-butoxy)tin, vinyltris(dimethylamino)tin, vinyltris(pyrrolidino)tin, 2-propenyltri(isopropoxy)tin, 2-propenyltri(tert-butoxy)tin, 2-propenyltris(dimethylamino)tin, 2-propenyltris(pyrrolidino)tin, 2-methyl-1-propenyltri(isopropoxy)tin, 2-methyl-1-propenyltri(tert-butoxy)tin, 2-methyl-1-propenyltris(dimethylamino)tin, 2-propenyltris(pyrrolidino)tin, vinyltri(1-propynyl)tin, isopropenyltri(1-propynyl)tin, isopropenyltris(dimethylamino)tin, 2-methyl-1-propenyltri(1-propynyl)tin, allyltri(isopropoxy)tin, allyltri(tert-butoxy)tin, allyltris(dimethylamino)tin, allyltris(pyrrolidino)tin, allyltri(1-propynyl)tin, 1-methylallyltri(isopropoxy)tin, 1-methylallyltri(tert-butoxy)tin, 1-methylallyltris(dimethylamino)tin, 1-methylallyltris(pyrrolidino)tin, or 1-methylallyltri(1-propynyl)tin, a method.

18. A precursor composition for forming an irradiation-sensitive resist film, wherein the precursor composition Formula M(R 6 ) 4 is a precursor, where M is a metal selected from the group consisting of lead, germanium, tin, and hafnium, R 6 each independently is aliphatic, alkylsilyl, amino, amide, azide, cyano, alkylcarbonyl, isocyanato, isothiocyanato, thiocyanato, alkoxy, heterocyclyl, haloaliphatic, aryl, or R 6 substituent components may be linked to form a ring, and at least one R 6 is a halo-containing substituent component, and includes a precursor the precursor forms a metal-oxo network resist film having a halo-containing substitution component, and the halo-containing substitution component forms a metal-halo bond when exposed to radiation, a precursor composition.

19. A method of processing a semiconductor substrate, wherein the method Formula M(R 6 ) 4 wherein M is a metal selected from the group consisting of lead, germanium, tin, and hafnium; and R 6 are each independently an aliphatic, alkylsilyl, amino, amido, azido, cyano, alkylcarbonyl, isothiocyanato, thiocyanato, alkoxy, heterocyclyl, haloaliphatic, aryl, or R 6 The substituent moieties may be linked to form a ring, and at least one R 6 forming a radiation-sensitive metal-oxo network resist film having a halo-containing substituted moiety by depositing a precursor, wherein patterned by extreme ultraviolet exposure of the irradiation-sensitive metal-oxo network resist film having a halo-containing substitution component to form a photo-patterned metal-halo bond-containing metal-oxo network resist film, a method.

20. The method according to claim 19, wherein A method further comprising forming a resist mask by dry-developing the photo-patterned metal-halo bond-containing metal-oxo network resist film.

21. The method according to claim 19, wherein the metal is tin.

22. The method according to claim 19, wherein the halo-containing substitution component is a β-halo-containing substitution component.

23. The method according to claim 21, wherein the precursor includes the structure of formula (II). 【Chemical 10】 In the formula, R 7 is C 2-6 haloaliphatic, and L is independently NR 8 R 9 or OR 10 and R 8 R 9 and R 10 are each independently hydrogen, alkylcarbonyl, or aliphatic, and R 8 substituent and R 9 substituents may be linked to form a ring Method.

24. The method according to claim 23, where L is NR respectively 8 R 9 a method

25. The method according to claim 24, wherein L is dimethylamino, tert-butylamino, diethylamino, ethylmethylamino, methylpropylamino, pyrrolidino, or piperidino.

26. A patterning radiation-sensitive film comprising an organometallic-oxo material, wherein the material comprises a metal, oxygen, and alkylsilyl, heterocyclyl, or aryl.

27. The film according to claim 26, wherein the alkylsilyl is trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, ethyldimethylsilyl, or triisopropylsilyl.

28. The film according to claim 26, wherein the aryl is phenyl, benzyl, or methylcyclopentadienyl.

29. The film according to claim 26, wherein the heterocyclyl is imidazolyl, pyrrolidinyl, pyridinyl, tetrahydrofuranyl, tetrahydropyranyl, or dioxanyl.

30. The film according to claim 26, wherein the organometallic-oxo material comprises a network of metal-oxygen bonds and metal-alkylsilyl bonds or metal-heterocyclyl bonds.

31. The film according to claim 26, wherein the patterning radiation-sensitive film comprises an extreme ultraviolet radiation-sensitive film.

32. The film according to claim 26, wherein the metal is tin.

33. A patterning radiation-sensitive film comprising an organotin-oxo material, wherein the organotin-oxo material Tin, oxygen, and C 5-6 An aliphatic or C 5-6 membrane containing a haloaliphatic.

34. The film according to claim 33, Said C 5-6 haloaliphatic is C 5-6 haloalkyl, C 5-6 haloalkenyl, or C 5-6 haloalkynyl, membrane.

35. The film according to claim 34, Said C 5-6 A film in which the haloaliphatic contains one or more halo-substituted components.

36. The film according to claim 33, Said C 5-6 A membrane in which the aliphatic group is pentyl, pentenyl, pentynyl, hexyl, hexenyl, or hexynyl.

37. The film according to claim 33, Said C 5-6 A film in which the aliphatic group is cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, or cyclohexadienyl.

38. The film according to claim 33, The material has a network of tin-oxygen bonds and tin-C 5-6 aliphatic bonds or tin-C 5-6 haloaliphatic bonds, a film.

Images