Development strategies for highly absorbing metal-containing photoresists.

Abstract

The present disclosure relates to the use of acids to develop or treat radiation sensitive films that contain two or more elements with high patterning radiation absorption cross sections. The acids can be used to form patterns by a negative tone development process or to treat developed patterns by further removing residual resist components.

Description

[Technical field]

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

[0002] The present disclosure relates to the use of acids to develop or treat radiation sensitive films that contain two or more elements with high patterning radiation absorption cross sections. The acids can be used to form patterns by a negative tone development process or to treat developed patterns by further removing residual resist components. [Background technology]

[0003] As semiconductor fabrication continues to advance, feature sizes continue to shrink, requiring new processing methods. One area where advances are being made is in the area of ​​patterning, for example, using photoresist materials that are sensitive to lithographic radiation.

[0004] The background description provided herein is intended to provide a general overview of the contents of the present disclosure. Work by the currently named inventors within the scope of what is described in this Background section, as well as aspects of the description that may not otherwise be regarded as prior art at the time of filing, are not admitted, expressly or impliedly, as prior art against the present disclosure. Summary of the Invention

[0005] Various embodiments herein relate to methods, materials, devices, and systems for developing or processing photoresist (PR) materials on a substrate. In particular, PR films contain two or more highly absorbing elements. Having such a combination of elements can enhance the absorbing properties of the film, but the elements can be difficult to remove or solubilize during development. Described herein are methods and processes for removing such films having two or more highly absorbing elements using acid (vapor or liquid form). Non-limiting examples of such elements include tin (Sn), indium (In), bismuth (Bi), antimony (Sb), tellurium (Te), their oxides, their alloys, or combinations thereof.

[0006] In one example, acid can be used to form a pattern by a negative tone development process. When negative tone development is used with organometallic photoresist (PR), radiation-exposed regions can be treated to provide a dense metal oxide (MOx)-containing network. Acid can be used as a dry or wet development process to remove non-exposed regions. The use of acid can assist in the removal of such regions even when such regions may have two or more different highly absorbing elements.

[0007] In another example, an acid can be used to treat the developed pattern by further removing residual resist components. The use of an acid can assist in the removal of residual species remaining after development, even if such species have two or more highly absorbing elements. For example, such residual species may include volatile metal species. Here, the acid can be provided as a dry processing process or a wet processing process.

[0008] Thus, in a first aspect, the disclosure features a method that includes exposing a radiation-sensitive resist film to a patterning radiation source to thereby provide an exposed resist film having exposed and unexposed regions, the resist film comprising two or more elements having a high patterning radiation absorption cross section, developing the exposed resist film by removing the unexposed regions, thereby forming a pattern by a negative tone development process, and optionally treating the pattern. In some embodiments, the method includes either performing said developing in the presence of an acid or performing said treating of the pattern in the presence of an acid.

[0009] In some embodiments, the method comprises carrying out said developing in the presence of an acid, hi certain embodiments, said developing comprises a dry development process.

[0010] In some embodiments, the developing comprises delivering acid vapor to the exposed film. Non-limiting acids include inorganic acids, halogen-containing acids, hydrogen halides, organic acids, phosphorus oxoacids, sulfur oxoacids, carboxylic acids, or silyl halides. In certain embodiments, the inorganic acid is selected from the group consisting of hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), and combinations thereof. In some embodiments, the organic acid comprises a vapor pressure of at least about 15 Torr. In other embodiments, the organic acid comprises formic acid, acetic acid, trifluoroacetic acid, or combinations thereof.

[0011] In some embodiments, the developing includes delivering a vapor of a reactant configured to provide an acid to the exposed film. Non-limiting reactants configured to provide an acid include borane halides including trichloroborane (BCl3), tribromoborane (BBr3), triiodoborane (BI3), silane halides including tetrachlorosilane (SiCl4), tetrabromosilane (SiBr4), tetraiodosilane (SiI4), trimethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl iodide, triethylsilyl chloride, triethylsilyl bromide, triethylsilyl iodide, tripropylsilyl chloride, tripropylsilyl bromide, iodine ... Tripropylsilyl chloride, Triisopropylsilyl chloride, Triisopropylsilyl bromide, Triisopropylsilyl iodide, Tributylsilyl chloride, Tributylsilyl bromide, Tributylsilyl iodide, Triisobutylsilyl chloride, Triisobutylsilyl bromide, Triisobutylsilyl iodide, Trisecbutylsilyl chloride, Trisecbutylsilyl bromide, Trisecbutylsilyl iodide, Tritertbutylsilyl chloride, Tritertbutylsilyl bromide, Tritertbutylsilyl iodide, Dimethyl-ethyl-silyl chloride, Dimethyl-ethyl-silyl chloride Methyl-propyl-silyl, Dimethyl-isopropyl-silyl chloride, Dimethyl-butyl-silyl chloride, Dimethyl-isobutyl-silyl chloride, Dimethyl-sec-butyl-silyl chloride, Dimethyl-tert-butyl-silyl chloride, Dimethyl-tert-butyl-silyl bromide, Dimethyl-tert-butyl-silyl iodide, Methyl-diethyl-silyl chloride, Methyl-diethyl-silyl bromide, Methyl-diethyl-silyl iodide, Methyl-dipropyl-silyl chloride, Methyl-diisopropyl-silyl chloride, Methyl-dibutyl-silyl chloride, Salts trialkylsilyl halides including methyl-diisobutyl-silyl chloride, methyl-disecbutyl-silyl chloride, methyl-ditertbutyl-silyl chloride, methyl-ditertbutyl-silyl bromide, and methyl-ditertbutyl-silyl iodide, dimethyldichlorosilane, dimethyldibromosilane, dimethyldiiodosilane, diethyldichlorosilane, diethyldibromosilane, diethyldiiodosilane, dipropyldichlorosilane, dipropyldibromosilane, dipropyldiiodosilane, and diisopropyldichlorosilane;Diisopropyldibromosilane, Diisopropyldiiodosilane, Dibutyldichlorosilane, Dibutyldibromosilane, Dibutyldiiodosilane, Diisobutyldichlorosilane, Diisobutyldibromosilane, Diisobutyldiiodosilane, Disecbutyldichlorosilane, Disecbutyldibromosilane, Disecbutyldiiodosilane, Ditertbutyldichlorosilane, Ditertbutyldibromosilane, Ditertbutyldiiodosilane, Methyl-ethyl-dichlorosilane , dialkyldihalosilanes including methyl-ethyl-dibromosilane, methyl-ethyl-diiodosilane, methyl-propyl-dichlorosilane, methyl-isopropyl-dichlorosilane, methyl-butyl-dichlorosilane, methyl-isobutyl-dichlorosilane, methyl-sec-butyl-dichlorosilane, methyl-tert-butyl-dichlorosilane, methyl-tert-butyl-dibromidosilane, methyl-tert-butyl-diiodosilane, or combinations thereof.

[0012] In some embodiments, the developing further comprises delivering a vapor of an oxygen-containing reagent. Non-limiting oxygen-containing reagents include oxygen (O), ozone (O), hydrogen peroxide (H2O2), or other reagents containing one or more oxygen atoms.

[0013] In some embodiments, the development comprises a wet development process. In certain embodiments, the development comprises delivering an acid in a solvent. Non-limiting acids include inorganic acids (e.g., hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), phosphoric acid, sulfuric acid, and combinations thereof), halogen-containing acids, hydrogen halides, organic acids (e.g., formic acid, acetic acid, trifluoroacetic acid, oxalic acid, citric acid, or combinations thereof), phosphorus oxoacids, sulfur oxoacids, carboxylic acids, any of those described herein, or any combinations thereof. Non-limiting solvents include aqueous or organic solvents such as water, alcohols, ketones, ethers, esters, or combinations thereof.

[0014] In some embodiments, the developing is performed at a temperature between about -10°C and 200°C to remove volatile products present in the non-exposed areas. In further embodiments, the method includes performing (e.g., after the developing) a plasma-based etching process. In other embodiments, the method includes performing (e.g., after the developing) a post-development bake (PDB).

[0015] In some embodiments, the method comprises carrying out said treating of the pattern in the presence of an acid, non-limiting acids include those described herein, such as inorganic acids, halogen-containing acids, hydrogen halides, organic acids, phosphorus oxoacids, sulfur oxoacids, carboxylic acids, or any combination thereof.

[0016] In some embodiments, the developing includes the use of an acid developer. Optionally, such an acid developer can be used to form a pattern, which can then be treated in the presence of an acid, as described herein. In certain embodiments, the developing includes the use of a vapor-based acid etchant. Non-limiting vapor-based acid etchants include hydrogen chloride (HCl), hydrogen bromide (HBr), boron trichloride (BCl3), silicon tetrachloride (SiCl4), a combination of hydrogen gas (H2) and chlorine gas (Cl2), or a combination of hydrogen gas (H2) and bromine gas (Br2), or trimethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl iodide, triethylsilyl chloride, triethylsilyl bromide, triethylsilyl iodide, tripropylsilyl chloride, tripropylsilyl bromide, or tripropylsilyl chloride. silyl, tripropylsilyl iodide, triisopropylsilyl chloride, triisopropylsilyl bromide, triisopropylsilyl iodide, tributylsilyl chloride, tributylsilyl bromide, tributylsilyl iodide, triisobutylsilyl chloride, triisobutylsilyl bromide, triisobutylsilyl iodide, trisecbutylsilyl chloride, trisecbutylsilyl bromide, trisecbutylsilyl iodide, tritertbutylsilyl chloride, tritertbutylsilyl bromide, tritertbutylsilyl iodide trialkylsilyl halides including butylsilyl, dimethyl-ethyl-silyl chloride, dimethyl-propyl-silyl chloride, dimethyl-isopropyl-silyl chloride, dimethyl-butyl-silyl chloride, dimethyl-isobutyl-silyl chloride, dimethyl-sec-butyl-silyl chloride, dimethyl-tert-butyl-silyl chloride, dimethyl-tert-butyl-silyl bromide, dimethyl-tert-butyl-silyl iodide, methyl-diethyl-silyl chloride, methyl-diethyl-silyl bromide, methyl-diethyl-silyl iodide, methyl-dipropyl-silyl chloride, methyl-diisopropyl-silyl chloride, methyl-dibutyl-silyl chloride, methyl-diisobutyl-silyl chloride, methyl-disec-butyl-silyl chloride, methyl-di-tert-butyl-silyl chloride, methyl-di-tert-butyl-silyl bromide, methyl-di-tert-butyl-silyl iodide, dimethyldichlorosilane, dimethyldibromosilane, dimethyldiiodosilane, diethyldichlorosilane, diethyldibromosilane,Diethyldiiodosilane, dipropyldichlorosilane, dipropyldibromosilane, dipropyldiiodosilane, diisopropyldichlorosilane, diisopropyldibromosilane, diisopropyldiiodosilane, dibutyldichlorosilane, dibutyldibromosilane, dibutyldiiodosilane, diisobutyldichlorosilane, diisobutyldibromosilane, diisobutyldiiodosilane, disecbutyldichlorosilane, disecbutyldibromosilane, disecbutyldiiodosilane, ditertbutyldichlorosilane, ditertbutyldibromosilane dialkyldihalosilanes including di-tert-butyldiiodosilane, methyl-ethyl-dichlorosilane, methyl-ethyl-dibromosilane, methyl-ethyl-diiodosilane, methyl-propyl-dichlorosilane, methyl-isopropyl-dichlorosilane, methyl-butyl-dichlorosilane, methyl-isobutyl-dichlorosilane, methyl-sec-butyl-dichlorosilane, methyl-tert-butyl-dichlorosilane, methyl-tert-butyl-dibromosilane, methyl-tert-butyl-diiodosilane, or combinations thereof.

[0017] In some embodiments, the treatment includes removing residual species including at least one of two or more elements having a high patterning radiation absorption cross section. In certain embodiments, the treatment includes a dry process. For example, the treatment can include delivering an acid vapor, or a reactant vapor configured to provide an acid, to the exposed film.

[0018] In other embodiments, the treatment comprises a wet process. In certain embodiments, the treatment comprises delivering an acid in a solvent. Non-limiting acids include inorganic acids, halogen-containing acids, hydrogen halides, organic acids, phosphorus oxoacids, sulfur oxoacids, carboxylic acids, any acid described herein, or any combination thereof.

[0019] In some embodiments, the method further comprises (e.g., after said treatment) rinsing the pattern with a solvent (e.g., any of the solvents described herein). After such rinsing, an optional drying operation can be performed.

[0020] In a second aspect, the present disclosure encompasses a method comprising exposing a radiation sensitive resist film to a patterning radiation source, thereby providing an exposed resist film having exposed and unexposed regions, the resist film comprising two or more elements having high patterning radiation absorption cross-sections; developing the exposed resist film by removing the unexposed regions with an acid, thereby forming a pattern by a negative tone dry development process; and treating the pattern with a plasma based etch process.

[0021] In some embodiments, the developing includes an oxygen-containing reagent (eg, any of those described herein).

[0022] In some embodiments, the method further comprises (eg, after said developing) performing a post-development bake (PDB).

[0023] In some embodiments, the resist film comprises an extreme ultraviolet (EUV) sensitive photoresist layer or an EUV sensitive inorganic photoresist layer, hi further embodiments, the patterning radiation source comprises an EUV radiation source.

[0024] In some embodiments, the method further comprises applying a radiation sensitive resist film on the surface of the substrate (e.g., prior to said exposure) and optionally providing a radiation absorbing layer between the resist film and the substrate, hi other embodiments, the method further comprises providing a radiation absorbing layer on the surface of the substrate (e.g., prior to said exposure).

[0025] In some embodiments, the method further comprises applying a radiation sensitive resist film on the surface of the radiation absorbing layer. In certain embodiments, the applying comprises delivering one or more precursors comprising a structure having formula (I), formula (II), or any precursor described herein to the surface of the substrate. In other embodiments, the applying comprises delivering a first precursor comprising tellurium (Te) and a second precursor comprising tin (Sn) to the surface of the substrate, the first and second precursors each being delivered to the substrate in any order or simultaneously.

[0026] In yet another embodiment, the providing of the radiation absorbing layer includes providing a first precursor and the applying of the radiation sensitive resist film includes providing a second precursor, the first precursor includes a first atom having a high EUV absorption cross section and the second precursor includes a second atom having a high EUV absorption cross section, the first atom and the second atom being different. In a particular embodiment, the first atom includes tellurium (Te), bismuth (Bi), indium (In), or antimony (Sb) and the second atom includes tin (Sn).

[0027] In a third aspect, the present disclosure encompasses an apparatus for processing a substrate, the apparatus including one or more process chambers, each process chamber optionally including a chuck or pedestal, one or more inlets to the process chambers and associated flow control hardware, and a controller having at least one processor and memory.

[0028] In some embodiments, the at least one processor and the memory are communicatively connected to each other, the at least one processor is at least operatively connected to the flow control hardware, and the memory stores computer-executable instructions for controlling the at least one processor to control at least the flow control hardware and to cause any of the methods described herein.

[0029] In a fourth aspect, the disclosure features an apparatus for forming a resist film, the apparatus including a deposition module, a patterning module, a development module, an optional processing module, and a controller including one or more memory devices, one or more processors, and system control software encoded with instructions, including machine-readable instructions.

[0030] In some embodiments, the deposition module includes a chamber for depositing a resist film (e.g., a patterned radiation sensitive film such as an EUV sensitive film), and the chamber can be configured to accommodate a semiconductor substrate. In other embodiments, the patterning module includes a photolithography tool having a radiation source with a wavelength of less than 300 nm (e.g., the source can be a radiation source with a wavelength of less than 30 nm). In some embodiments, the development module includes a chamber for developing the resist film. In other embodiments, the processing module includes a chamber for processing the resist film (e.g., a resist film having a pattern).

[0031] In further embodiments, the instructions include machine-readable instructions for causing deposition of the precursor in the presence of an optional counter-reactant on a top surface of the semiconductor substrate (e.g., in a deposition module) to form a resist film, hi some embodiments, such deposition can form a patterned radiation-sensitive film as the resist film.

[0032] In some embodiments, the instructions include machine-readable instructions for causing patterning of the resist film directly by patterning radiation exposure (e.g., by EUV exposure) at a resolution of less than 300 nm (e.g., or at a resolution of less than 30 nm) (e.g., in a patterning module), thereby forming an exposed film having radiation exposed areas and radiation non-exposed areas. In other embodiments, the exposed film has EUV exposed areas and EUV non-exposed areas.

[0033] In other embodiments, the instructions include machine-readable instructions for causing development of the film (e.g., in a developing module) to remove radiation exposed or non-radiation exposed areas to provide a pattern in the resist film. In certain embodiments, the machine-readable instructions include instructions for causing removal of EUV exposed or non-EUV exposed areas. In some embodiments, such developing can include delivering one or more acids to the developing module.

[0034] In yet other embodiments, the instructions include machine-readable instructions for causing treatment of the membrane (e.g., in a treatment module) to remove residual species from the membrane, in some embodiments, such treatment can include delivering one or more acids to the treatment module.

[0035] In any embodiment herein, the acid comprises an inorganic acid, a halogen-containing acid, a hydrogen halide, an inorganic acid, a phosphorus oxoacid, a sulfur oxoacid, or a carboxylic acid. Such acids can be provided in a dry process (e.g., as a vapor) or a wet process (e.g., as a liquid).

[0036] In any embodiment herein, the reactant configured to provide an acid may include borane halides including trichloroborane (BCl3), tribromoborane (BBr3), and triiodoborane (BI3), silane halides including tetrachlorosilane (SiCl4), tetrabromosilane (SiBr4), and tetraiodosilane (SiI4), trimethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl iodide, triethylsilyl chloride, triethylsilyl bromide, triethylsilyl iodide, tripropylsilyl chloride, tripropylsilyl bromide, and iodide. Tripropylsilyl, Triisopropylsilyl chloride, Triisopropylsilyl bromide, Triisopropylsilyl iodide, Tributylsilyl chloride, Tributylsilyl bromide, Tributylsilyl iodide, Triisobutylsilyl chloride, Triisobutylsilyl bromide, Triisobutylsilyl iodide, Trisecbutylsilyl chloride, Trisecbutylsilyl bromide, Trisecbutylsilyl iodide, Tritertbutylsilyl chloride, Tritertbutylsilyl bromide, Tritertbutylsilyl iodide, Dimethyl-ethyl-silyl chloride, Dimethyl-propyl-silyl chloride, Dimethyl-isopropyl-silyl, Dimethyl-butyl-silyl chloride, Dimethyl-isobutyl-silyl chloride, Dimethyl-sec-butyl-silyl chloride, Dimethyl-tert-butyl-silyl chloride, Dimethyl-tert-butyl-silyl bromide, Dimethyl-tert-butyl-silyl iodide, Methyl-diethyl-silyl chloride, Methyl-diethyl-silyl bromide, Methyl-diethyl-silyl iodide, Methyl-dipropyl-silyl chloride, Methyl-diisopropyl-silyl chloride, Methyl-dibutyl-silyl chloride, Methyl-diisobutyl-silyl chloride, Methyl-disec-butyl-silyl chloride trialkylsilyl halides including methyldi-tert-butyl-silyl chloride, methyldi-tert-butyl-silyl bromide, and methyldi-tert-butyl-silyl iodide, dimethyldichlorosilane, dimethyldibromosilane, dimethyldiiodosilane, diethyldichlorosilane, diethyldibromosilane, diethyldiiodosilane, dipropyldichlorosilane, dipropyldibromosilane, dipropyldiiodosilane, diisopropyldichlorosilane, diisopropyldibromosilane, diisopropyldiiodosilane, dibutyldichlorosilane,Dialkyldihalosilanes including dibutyldibromosilane, dibutyldiiodosilane, diisobutyldichlorosilane, diisobutyldibromosilane, diisobutyldiiodosilane, disecbutyldichlorosilane, disecbutyldibromosilane, disecbutyldiiodosilane, ditertbutyldichlorosilane, ditertbutyldibromosilane, ditertbutyldiiodosilane, methyl-ethyl-dichlorosilane, methyl-ethyl-dibromosilane, methyl-ethyl-diiodosilane, methyl-propyl-dichlorosilane, methyl-isopropyl-dichlorosilane, methyl-butyl-dichlorosilane, methyl-isobutyl-dichlorosilane, methyl-secbutyl-dichlorosilane, methyl-tertbutyl-dichlorosilane, methyl-tertbutyl-dibromidosilane, methyl-tertbutyl-diiodosilane, or combinations thereof. Other reactants are further described herein.

[0037] In any embodiment herein, the patterning radiation sensitive film comprises an extreme ultraviolet (EUV) sensitive film, an EUV sensitive inorganic photoresist layer, a deep ultraviolet (DUV) sensitive film, a photoresist film, or a photopatternable film.

[0038] In any embodiment herein, the resist film includes tin (Sn), indium (In), bismuth (Bi), antimony (Sb), tellurium (Te), an oxide thereof, an alloy thereof, or a combination thereof.

[0039] In any embodiment herein, the resist film comprises a chemical vapor deposition (CVD) film, a spin-on film, an organometallic oxide film, an organometallic oxide hydroxide film, a tin oxide film, or an organotin oxide film.

[0040] In any embodiment herein, the precursor (e.g., for providing a resist film) is represented by formula (I): M a R b (I),

[0023] The present invention includes a structure having the following structure: M is a metal or atom with a high EUV absorption cross section, and each R is independently H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, anionic ligand, neutral ligand, or multidentate ligand, and a≧1, and b≧1.

[0041] In any embodiment herein, the precursor (e.g., for providing a resist film) is represented by formula (II): M a R b L c (II)

[0023] The present invention includes a structure having the following structure: M is a metal or atom with a high EUV absorption cross section; each R is independently halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L, where each L is independently a ligand, anionic ligand, neutral ligand, multidentate ligand, ion, or other moiety that reacts with a reverse reactant; R and L, together with M, can optionally form a heterocyclyl group, or R and L, together, can optionally form a heterocyclyl group, where a>1, b>1, and c>1.

[0042] In any of the embodiments herein, the precursor (e.g., for providing a resist film) comprises one or more precursors selected from the following: InR3, where R is independently halo, optionally substituted C 1-12 alkyl, or diketonate, SnR2 or SnR4, each R being independently halo, optionally substituted C 1-12alkoxy, optionally substituted amino, optionally substituted aryl, cyclopentadienyl, or diketonate; BiR, R, are independently halo, optionally substituted C 1-12 Alkyl, mono-C 1-12 Alkylamino, Di-C 1-12 alkylamino, optionally substituted aryl, optionally substituted bis(trialkylsilyl)amino, or diketonate; SbR, each R is independently halo, optionally substituted C 1-12 Alkyl, optionally substituted C 1-12 alkoxy, or optionally substituted amino; or TeR2 or TeR4, each R being independently halo, optionally substituted C 1-12 Alkyl, optionally substituted C 1-12 It is alkoxy, optionally substituted aryl, hydroxyl, oxo, or optionally substituted trialkylsilyl.

[0043] In any of the embodiments herein, providing a resist film or depositing a resist film further comprises providing a reverse reactant. Non-limiting reverse reactants include oxygen or chalcogenide precursors, as well as any of those described herein (e.g., oxygen-containing reverse reactants including oxygen (O2), ozone (O3), water, peroxides, hydrogen peroxide, oxygen plasma, water plasma, alcohols, dihydroxy alcohols, polyhydroxy alcohols, fluorinated dihydroxy alcohols, fluorinated polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, and combinations thereof).

[0044] Other features and advantages of the disclosure will become apparent from the following description and from the claims. [Brief description of the drawings]

[0045] [Figure 1A]1A is a schematic diagram of a non-limiting patterning structure. Shown is a structure having a substrate 101 and a homogeneous film 102 with a relatively low EUV absorption of 30%. [Figure 1B] 1B is a schematic diagram of a non-limiting patterning structure. Shown is another structure having a substrate 111 and a homogeneous film 112 with a relatively high EUV absorption of 90%. [Figure 1C] 1C is a schematic diagram of a non-limiting patterning structure. A structure having a substrate 121 and a gradient film 122 is shown. [Figure 1D] 1D is a schematic diagram of a non-limiting patterned structure. Shown is a structure having a substrate 131, a membrane 132, and a radiation absorbing layer 133 beneath the membrane 132.

[0046] [Figure 1E] 1E is a non-limiting graph showing extreme ultraviolet (EUV) light absorption cross sections for various elements. Absorption of EUV light (92 eV, 13.5 nm) associated with excitation of inner shell electrons may be largely independent of chemical bonds.

[0047] [Figure 2A] FIG. 2A is a schematic diagram of a non-limiting method for making and using a patterning structure. [Figure 2B] FIG. 2B is a schematic diagram of a non-limiting method for making and using a patterning structure. [Figure 2C] FIG. 2C is a schematic diagram of a non-limiting method for making and using a patterning structure.

[0048] [Figure 3A] FIG. 3A illustrates a reaction scheme between a non-limiting first precursor and a non-limiting second precursor. [Figure 3B] FIG. 3B illustrates a reaction scheme between a non-limiting first precursor and a non-limiting second precursor. [Figure 3C]FIG. 3C illustrates a reaction scheme between a non-limiting first precursor and a non-limiting second precursor. [Figure 3D] FIG. 3D illustrates a reaction scheme between a non-limiting first precursor and a non-limiting second precursor.

[0049] [Figure 4A] 4A is a schematic diagram of a non-limiting method of using acid with a resist film. A non-limiting method 400 is shown that uses a negative tone development process with acid. [Figure 4B] 4B is a schematic diagram of a non-limiting method of using acid with a resist film. Another non-limiting method 450 is shown that uses a negative tone development process followed by treatment with acid.

[0050] [Figure 5A] FIG. 5A is a schematic block diagram of a non-limiting method for making and using a resist film. [Figure 5B] FIG. 5B is a schematic block diagram of a non-limiting method for making and using the resist film. [Figure 5C] FIG. 5C is a schematic block diagram of a non-limiting method for making and using the resist film. [Figure 5D] FIG. 5D is a schematic block diagram of a non-limiting method for making and using a resist film. [Figure 5E] FIG. 5E is a schematic block diagram of a non-limiting method for making and using a resist film.

[0051] [Figure 6] FIG. 6 is a schematic diagram of one embodiment of a process station 600 for dry development.

[0052] [Figure 7] FIG. 7 is a schematic diagram of one embodiment of a multi-station processing tool 700 .

[0053] [Figure 8] FIG. 8 is a schematic diagram of one embodiment of an inductively coupled plasma device 800 .

[0054] [Figure 9] FIG. 9 is a schematic diagram of one embodiment of a semiconductor process cluster tool architecture 900.

[0055] [Figure 10] FIG. 10 is a cross-sectional schematic diagram of an example dry deposition apparatus 1000 . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0056] Reference will be made in detail herein to certain embodiments of the present disclosure. Examples of certain embodiments are illustrated in the accompanying drawings. Although the present disclosure will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the present disclosure to such specific embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the present disclosure. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. The present disclosure may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the present disclosure.

[0057] The present disclosure relates to a method for treating a photoresist (PR) film containing two or more highly absorbing elements. Different atoms may exhibit different sensitivities to radiation absorption. By increasing the concentration of the highly absorbing elements in the film, the absorbing properties of the film can be enhanced. Non-limiting examples of such elements include tin (Sn), indium (In), bismuth (Bi), antimony (Sb), tellurium (Te), and other elements described herein. Such films can also be configured to include an absorbing layer containing the elements, and the methods and processes herein can be used to develop films having such absorbing layers.

[0058] Another strategy that can further improve radiation sensitivity in PR films is to form films in which the film composition is vertically graded, resulting in a depth-dependent radiation sensitivity. In homogeneous PRs with high absorption coefficients, the light intensity decreases throughout the depth of the film, so a higher radiation dose can be used to ensure that the bottom is adequately exposed. By increasing the density of atoms with high radiation absorption at the bottom of the film compared to the top of the film (e.g., by forming a gradient with increasing radiation absorption), it becomes possible to more efficiently use available photons while distributing the absorption (and secondary electron effects) more uniformly toward the bottom of the more absorbing film. The methods and processes herein can be used to develop such gradient films. Other examples of patterned structures and films are described in Figures 1A-1D.

[0059] In particular, the methods herein use acids as part of a dry or wet process to develop or treat films having two or more highly absorbing elements. The presence of two or more different elements can improve radiation absorption, but it can be difficult to remove undesired regions containing such elements. Take the example of a bimetallic film having two elements (e.g., tin (Sn) and tellurium (Te)), the Te-containing species can be difficult to remove because it can exhibit low volatility. Furthermore, most solvents do not dissolve both the Sn-containing and Te-containing species. Acid-containing development processes (e.g., to remove radiation-unexposed regions) and acid-containing treatment processes (e.g., to remove residual metal-containing species after development) are described herein, and such processes can be wet or dry.

[0060] In one non-limiting embodiment, the present disclosure encompasses a dry development method for highly absorbing metal-containing photoresist (PR) films (e.g., bimetallic PR including Sn and Te). In a particular non-limiting embodiment, the PR films are used in conjunction with extreme ultraviolet (EUV) lithography. The presence of such highly absorbing metal elements (e.g., Te, antimony (Sb), bismuth (Bi), etc.) incorporated into the film may further enhance EUV absorption and reduce lithography costs.

[0061] The incorporation of new elements generally alters the composition and properties of the PR, and such alterations may require additional development methods. By using vapors of acids (e.g., inorganic acids; hydrogen halides such as hydrogen chloride (HCl), hydrogen bromide (HBr); organic acids such as trifluoroacetic acid, or others described herein), such bimetallic PR films (or other films with two or more highly absorbing elements) can be developed, thereby producing negative-tone patterns.

[0062] In some embodiments, developing includes providing a vapor containing an acid or a vapor containing a reactant configured to provide an acid. Non-limiting acids and reagents are described herein. In one example, the acid includes a halogen-containing acid (e.g., HBr, HCl, HI, HF, etc.), and the reagent includes those capable of providing such an acid. Examples of such reagents include boron halides (e.g., BX3, where X is F, Cl, Br, or I), silicon halides (e.g., SiX4, where X is F, Cl, Br, or I), hydrogen halides (e.g., HX, where X is F, Cl, Br, or I), hydrogen gas (H2), and halogen gas (e.g., X2, where X is F, Cl, or Br), and combinations thereof (e.g., a combination of H2 and X2).

[0063] In one embodiment, vapors of inorganic acid molecules (such as HCl, HBr, and possibly HI), as well as molecules that can decompose or hydrolyze to produce these acid molecules (e.g., BCl3 or SiCl4), can selectively remove unexposed films (e.g., unexposed organotin tellurium films), thereby producing negative-tone patterns. However, reaction products of certain elements (e.g., tellurium halides such as TeCl2 and / or TeBr2) have much lower volatility than other elements (e.g., tin halides such as SnCl4 and / or SnBr4). Less volatile species can be removed by using higher temperatures during deposition (e.g., up to 200° C.) or during a hard bake step after development to vaporize the reaction products.

[0064] In addition to inorganic acid molecules, the acid may be an organic acid. In certain embodiments, the acid has a high vapor pressure and selectively removes the unexposed film. Non-limiting examples of organic acids include trifluoroacetic acid, formic acid, acetic acid, and the like.

[0065] In certain embodiments, development can include the use of an acid in combination with an oxygen-containing reagent (e.g., oxygen gas (O), ozone (O), hydrogen peroxide (HO), etc.) to obtain more consistent etching results.

[0066] Any useful process conditions can be applied during development. For example, the process may be carried out at a pressure of less than about 3 Torr (e.g., 10 mTorr to 2 Torr, etc.), a temperature of about -10°C to 150°C (e.g., -10°C to 100°C or 0°C to 150°C), and a flow rate of 1 to 1000 standard cubic centimeters per minute (sccm), e.g., about 1 to 500 sccm.

[0067] Further, development may include any useful temperature. For a dry development process, operating temperatures may include temperatures up to 150° C. to remove volatile reaction products (e.g., tellurium halides, tellurium acetates, and other metal- or metalloid-containing species) in the unexposed areas. In another embodiment, the process may include a post-development bake (PDB) operation (e.g., PDB at temperatures up to 250° C.) for more volatile species.

[0068] Due to the low volatility of some metal or metalloid containing species, the dry development process may leave residual resist components on the substrate. A plasma-based etching operation may optionally be performed after development to remove such components. The plasma may include any of the following useful chemicals, inert gases, or reactive gases: fluorocarbons (C x F y H z (x is 1 to 6, y is 1 to 12, and z is 0 to 12), C x F y (wherein x is 1 to 6 and y is 2 to 12), carbon tetrafluoride (CF4), hexafluoro-2-butyne (C4F6), fluoromethane (CH3F), difluoromethane (CH2F2), trifluoromethane (CHF3), octafluorocyclobutane (C4F8), and combinations thereof; hydrogen (H2); boron-containing gases, such as boron chloride (BCl3), boron trifluoride (BF3), borane (BH3), diborane (B2H6), and the like; halogens hydrogen chloride (HCl), hydrogen bromide (HBr), etc.; halogen-containing gases, such as chlorine (Cl2), nitrogen trifluoride (NF3), bromine (Br2), fluorine (F2), etc.; oxygen-containing gases, such as oxygen (O2), ozone (O3), carbon dioxide (CO2), carbon monoxide (CO), nitrous oxide (N2O), nitric oxide (NO), etc.; inert gases, such as argon (Ar), nitrogen (N2), helium (He), krypton (Kr), etc.; and combinations thereof.

[0069] Such plasma can be a remote plasma or an in situ plasma, which may be an inductively coupled plasma (ICP) or a capacitively coupled plasma (CCP). Additional plasma conditions include any of those described herein, including an ICP set at about 50 W to about 2000 W plasma, an applied bias of about 0 V to 500 V.

[0070] In one non-limiting embodiment, the methods and processes herein encompass all dry processes in which deposition, exposure, and development include only dry processes. In another embodiment, the methods and processes include dry deposition, dry exposure, dry development, and dry processing of the developed pattern. In still other embodiments, one or more wet processes may be performed, such as a method comprising dry deposition, dry exposure, and wet development, a method comprising wet deposition, dry exposure, and dry development, a method comprising wet deposition, dry exposure, and wet development, a method comprising dry deposition, dry exposure, wet development, and wet processing of the developed pattern, a method comprising dry deposition, dry exposure, wet development, and dry processing of the developed pattern, a method comprising wet deposition, dry exposure, dry development, and wet processing of the developed pattern, a method comprising wet deposition, dry exposure, wet development, and wet processing of the developed pattern, a method comprising wet deposition, dry exposure, wet development, and wet processing of the developed pattern, and a method comprising wet deposition, dry exposure, wet development, and dry processing of the developed pattern.

[0071] In another non-limiting embodiment, the present disclosure encompasses a wet development method for highly absorbing metal-containing PR films (e.g., bimetallic PRs containing Sn and Te). In particular, the wet development includes delivering an acid in a solvent to the film. Non-limiting acids and solvents include any of those described herein. In one embodiment, the acid is an inorganic acid, a halogen-containing acid, a hydrogen halide, an organic acid, a phosphorus oxoacid, a sulfur oxoacid, a carboxylic acid, or a silyl halide. In another embodiment, the solvent is an aqueous solvent, an organic solvent, and combinations or mixtures thereof.

[0072] By using acid solutions in different solvents or solvent mixtures, this highly absorbing PR film can be developed, thereby producing negative tone patterns. Both the acid concentration and the type of solvent / solvent mixture can affect the selectivity, etch rate and therefore the exposure sensitivity of the resist.

[0073] Without wishing to be limited by mechanism, the wet development strategy for this type of high absorbing resist relies on a solubility switch upon exposure and post-exposure bake (PEB). For example, it has been demonstrated that incorporating elements such as Te into the film increases EUV absorption compared to films lacking Te. However, both unexposed and exposed Sn-Te films may be insoluble in most common organic solvents. It is described herein that acid solutions in different solvents or solvent mixtures can selectively remove unexposed SnTe resist material, thereby generating negative tone patterns. Such acid solutions can be used for any of the films described herein that contain two or more highly absorbing elements. In some non-limiting embodiments, the wet development includes a PEB operation.

[0074] Non-limiting acids include any of those described herein. In one embodiment, the acid is an inorganic acid, such as a hydrogen halide, a phosphorus oxoacid, or a sulfur oxoacid, which have shown selectivity and higher etch rates at concentrations of about 0.01% (v / v) or higher. Weaker acids, such as organic acids, can be used at higher concentrations (e.g., up to about 10% (v / v) or 15% (v / v) of acid in solvent).

[0075] Various solvents can be combined in one or more acids. Both aqueous solvents with the above-mentioned acids and various organic solvents (e.g., isopropyl alcohol (IPA), 2-heptanone, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), n-butyl acetate, etc.) can function as wet developers. The choice of solvent / solvent mixture can affect the selectivity and etch rate. Further non-limiting solvents include alcohols (e.g., isopropyl alcohol (IPA)), ketones (e.g., 2-heptanone, cyclohexanone, or acetone), esters (e.g., n-butyl acetate, γ-butyrolactone, or ethyl 3-ethoxypropionate (EEP)), or ethers, such as glycol ethers (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA)), as well as combinations thereof.

[0076] Patterning Structure The methods and processes herein can be used to develop or treat the resist films described herein. In one embodiment, the resist film is provided in a patterning structure, where the patterning structure includes a resist film (or imaging layer) disposed on a surface of a substrate. In another embodiment, the patterning structure includes a resist film, a substrate, and a radiation absorbing layer disposed between the resist film and the substrate. In certain embodiments, the presence of the radiation absorbing layer increases the radiation absorptivity and / or patterning performance of the resist film. In another embodiment, the resist film includes atoms that increase the radiation absorptivity and / or patterning performance.

[0077] In general, the absorption of photons through a layer is depth dependent. When a homogeneous layer or film is exposed to radiation, the lower portion of the layer is exposed to a lower dose of radiation compared to the upper portion of that same layer because fewer photons reach the lower portion. Thus, to ensure sufficient and uniform exposure throughout the depth of the layer, the layer must provide sufficient penetration of the radiation. As seen in FIG. 1A, a homogeneous resist film 102 is disposed on the top surface of a substrate 101. When exposed to radiation, the light absorption 105 through the homogeneous layer is depth dependent, having a lower value 105a toward the substrate (and in the lower portion of the layer 102) and a higher value 105b away from the substrate (and in the upper portion of the layer 102). In one non-limiting example, the resist film 102 in FIG. 1A is a homogeneous organic tin oxide photoresist with a relatively low EUV absorption of 30% and a transmission of 70%.

[0078] To increase the adsorption, one strategy can include using a material with higher absorption of radiation. However, such a strategy can result in a less effective resistor. For example, the patterning structure in FIG. 1B can be a homogenous film 112 with a relatively high EUV absorption of 90% and a transmittance of 10%. This photoresist is generally less effective for patterning applications because the EUV absorption and resulting chemicals are biased toward the top of the photoresist.

[0079] Another strategy that can further improve EUV sensitivity in resist films is to form films in which the film composition is vertically graded, resulting in a depth-dependent EUV sensitivity. A homogeneous PR with a high absorption coefficient would require a higher EUV dose to ensure that the bottom is adequately exposed, due to the decrease in light intensity throughout the film's depth. By increasing the density of atoms with high EUV absorptivity at the bottom of the film compared to the top of the film (e.g., by forming a gradient with increasing EUV absorption), it would be possible to more efficiently use the available EUV photons while more uniformly distributing the absorption (and secondary electron effects) towards the bottom of the more absorbing film.

[0080] The graded film can include any useful atomic or concentration gradient. In one example, the graded film is characterized by at least a first concentration of a first metal (M1) and a second concentration of a second metal (M2), where M1 and M2 are different. In another example, the graded film is characterized by a concentration gradient of one or more atoms having a high EUV absorption cross-section. In yet another example, the graded film is characterized by a concentration of the first metal (M1) that varies vertically across the film layer. Non-limiting atoms having a high EUV absorption cross-section include iodine (I), tellurium (Te), indium (In), tin (Sn), antimony (Sb), bismuth (Bi), or combinations thereof. In yet another example, the graded film is characterized by a concentration gradient of carbon content (e.g., alkyl content).

[0081] 1C shows an exemplary patterning structure having a graded film. In particular, the structure can include a substrate 121 (e.g., a semiconductor substrate) having an upper surface and a film 122 disposed on the upper surface of the substrate 121, the film 122 having a vertical gradient characterized by a change in EUV absorbance and / or metal content and / or metal type. When exposed to radiation, the optical absorption 125 through the graded layer is depth dependent, having a lower value 125a toward the substrate (and in the lower portion of the layer 122) and a higher value 125b away from the substrate (and in the upper portion of the layer 122). Overall, the gradient provides a more uniform absorption 125 between the upper and lower portions of the resist layer 122.

[0082] In one example, the graded film 122 can include a first concentration of a first metal (M1) at a top portion of the film and a second concentration of a second metal (M2) at a bottom portion of the film, where M1 and M2 are different. In one example, the first concentration is higher than the second concentration. In another example, the first concentration is lower than the second concentration. Non-limiting gradients include linear gradients, exponential gradients, sigmoidal gradients, and the like. In certain embodiments, a gradient density film of EUV-responsive organic moieties can result in more uniform film properties of the EUV-exposed region at all depths within the film, which can improve the development process, improve EUV sensitivity, and / or improve patterning quality (e.g., improved line width roughness (LWR) and / or line edge roughness (LER)).

[0083] In many cases, the resist material deposited on the substrate includes a compositional gradient along the thickness of the resist film. In some such cases, the photoresist material includes M2 in addition to M1, where M2 is a metal with a high EUV absorption cross section and is different from M1, and the compositional gradient in the photoresist material results in different M1:M2 ratios at different vertical positions within the photoresist material. In some embodiments, the compositional gradient in the resist material may result in different M1:R (ligand) ratios at different vertical positions within the resist material. In some such cases, the percentage of metal atoms bonded to R may vary at different vertical positions within the photoresist material.

[0084] In some embodiments, the composition gradient in the photoresist material may result in different concentrations of iodine (I), tellurium (Te), or another atom with a high radiation absorption cross section at different vertical positions within the photoresist material. In various embodiments, the composition gradient may provide a higher density of a high EUV absorbing element at the bottom of the photoresist material compared to the top of the photoresist material, the bottom being deposited before the top. I and Te may be introduced in any useful manner. In one example, iodine may be introduced as hydrogen iodide (HI) or a suitable alkyl iodide during deposition of a precursor, and the flow rate of the iodine source may be varied throughout the deposition or may be introduced at specific times during the deposition. In another example, iodine may be introduced as iodine vapor (I2) in the presence of an optional plasma. In yet another example, tellurium may be introduced as a precursor or a reverse reactant during deposition, and the flow rate of the tellurium source may be varied throughout the deposition or may be introduced at specific times during the deposition.

[0085] A similar strategy (also using tris(t-butoxy)isopropyltin and water as the base chemical) can be used for gradient introduction of iodine using low concentrations of HI (or an appropriate alkyl iodide) with water to achieve gradient doping with iodine near the interface. Other Sn-containing precursors and I-containing reactants can be used in this manner.

[0086] Yet another strategy involves the introduction of an alternative (or additional) counter reactant into the water to introduce an element with a much higher EUV absorption coefficient than oxygen. One example is the incorporation of tellurium, where a Te-containing reactant provides a viable option as a gas-phase counter reactant. As deposition progresses, the ratio of Te-containing counter reactant:Sn-containing precursor may decrease, thereby forming a film that is relatively low in Te and relatively rich in Sn compared to the initial portion of the film. In various embodiments, the film may transition to a Te-free composition near the top surface of the film, for example to help minimize contamination and handling issues.

[0087] Strategies to manipulate vertical compositional gradients in resist films are particularly applicable to dry deposition methods such as CVD and ALD, and can be achieved by adjusting the flow ratio between different reactants (or precursors) during deposition. Types of compositional gradients that can be manipulated include the ratio between different highly absorbing metals, the fraction of metal atoms with EUV-cleavable bulky groups (or related, the ratio between metal atoms and EUV-cleavable bulky groups), the fraction of bulky groups or back reactants that contain highly absorbing elements (such as Te and I) (or related, the ratio between metal atoms and additional highly absorbing elements such as Te and I), and combinations thereof.

[0088] In one embodiment, the resist film 122 of FIG. 1C is a graded tin-based EUV photoresist with a compositional gradient that results in an overall EUV absorption of 60% and a transmittance of 40%. The increased EUV absorption gradient provided by the compositional gradient of FIG. 1C results in a more uniform absorption throughout the thickness of the resist film 122. The gradient can be based on alkyl content, and the inclusion of regions with higher SnO2-like properties can increase EUV absorption within the film. All of the examples given have increasing Sn-alkyl content toward the surface of the film, although the concept of having stacked layers of alternating Sn-alkyl heavy and Sn-alkyl light regions is also envisioned.

[0089] One example of producing a graded Sn-based resist with various alkyl groups involves the use of tetrakis(dimethylamino)tin and isopropyltris(dimethylamino)tin precursors and water as the back reactant. Tetrakis(dimethylamino)tin is initially introduced as a small to significant amount of component, which can produce a relatively high density of Sn components (essentially SnO2 and Sn-OH derivatives) that are not bonded to alkyl groups. The ratio of tetrakis(dimethylamino)tin:isopropyltris(dimethylamino)tin precursors can be decreased as the film grows. This can produce films with increasing amounts of Sn-R bonds in the film toward the upper surface of the film. (An example of increased absorption in a film produced by this process is described below). This process can be carried out by either ALD or CVD methods.

[0090] A related approach involving an absorption gradient targets the use of somewhat tin-based resist films using two precursors, both of which have alkyl groups, but one containing one or more alkyl ligands than the other. For example, isopropyltris(dimethylamino)tin and diisopropyldi(dimethylamino)tin can be used. Initially, a flow of diisopropyldi(dimethylamino)tin is introduced during film deposition, and the ratio increases compared to the isopropyltris(dimethylamino)tin flow as the film is deposited. This results in a film with a higher amount of Sn attached to the two alkyl groups on the surface compared to the bottom of the film.

[0091] Another method of forming a graded film involves the use of a plasma to remove some of the alkyl groups bonded to the metal center during the initial deposition of the film. For example, Sn-alkyl bonds are easily cleaved in the presence of a plasma, either by vacuum ultraviolet (VUV) light or by bombardment of electrons or ions from the plasma. Ideally, a plasma is used whose conditions simply remove the alkyl groups but do not etch the film. For example, O2, Ar, He, or CO2 plasmas may be used. As the film is deposited, the efficiency of the plasma to remove the alkyl groups decreases (i.e., the power of the plasma is reduced) and is eventually turned off. This can result in a graded film with more M-alkyl bonds at the surface of the film than at the bottom of the film.

[0092] Compositional gradients in EUV resist films can provide a variety of benefits. For example, a high density of highly EUV absorbing elements at the bottom of the film can effectively generate more secondary electrons and provide better exposure than the upper portion of the film. In addition, such compositional gradients can also directly correlate to a higher proportion of EUV absorbing species that are not attached to bulky terminal substituents. For example, in the case of Sn-based resists, the incorporation of tin precursors with four leaving groups can be used, which promotes the formation of Sn-O-substrate bonds at the interface to improve adhesion.

[0093] The use of a radiation absorbing layer beneath the resist film can increase radiation absorption through the resist film. For example, providing an absorbing layer with an increased density of atoms with high EUV absorption at the bottom of the film compared to the resist film allows for more efficient use of available EUV photons while distributing the absorption (and secondary electron contribution) more evenly toward the bottom of the patterned structure. Additionally, in some cases, the absorbing layer can effectively generate more secondary electrons, thereby better exposing the lower portions of the patterned structure.

[0094] As seen in FIG. 1D, the patterned structure may include a resist film 132, as well as a radiation absorbing layer 133 below the resist film 132 and above the substrate 131. Compared to a structure without an absorbing layer, the light absorption between the lower portion 135a and the upper portion 135b of the layer 132 may be more uniform. When exposed to radiation, the light absorption 135 through the layer may be affected by the absorbing layer 133, resulting in the creation of an additional secondary electrode 134 that may assist in the radiation exposure of the bottom of the resist film. In this way, it is possible to improve the light absorption 135 compared to the light absorption in a resist film without an absorbing layer.

[0095] The absorbing layer can include elements (e.g., metal atoms or non-metal atoms) with high optical absorption cross sections (or high absorbing elements), such as I, Te, In, Sn, Sb, and / or Bi. The absorbing layer can also include EUV labile groups, which can also be altered, such as the alkyl group C n H 2n+1 (preferably n≧3) and may include fluorine-substituted alkyl groups. Such elements and labile groups can be provided as layers in any useful manner, such as sputter deposition, physical vapor deposition (PVD), including PVD co-sputtering, chemical vapor deposition (CVD), plasma-enhanced CVD (PE-CVD), low pressure CVD (LP-CVD), atomic layer deposition (ALD, including thermal ALD and plasma-enhanced ALD (PE-ALD)), spin-coat deposition, plasma-based deposition, thermally induced decomposition, plasma-induced decomposition, e-beam deposition, including electron beam (e-beam) co-evaporation, or combinations thereof using one or more precursors (e.g., any of those described herein). The absorbing layer can be a photoresist layer or a surface modification layer disposed on the surface of the substrate.

[0096] One or both of the absorber layer and the resist film may include a highly absorbing element. In one example, both the absorber layer and the resist film include a highly absorbing element. The elements in each of the absorber layer and the resist film may be the same or different.

[0097] In certain non-limiting examples, the absorbing layer is characterized by having an increased radiation absorption rate compared to the resist film. For example, the absorbing layer can include a higher percentage of EUV absorbing species that are not attached to bulky terminal substituents. In another example, the absorbing layer can include an element that has a higher absorption coefficient than the element present in the resist film. For example, the resist film can include Sn and the absorbing layer can include Te (e.g., Te alone or a mixture of Te and Sn). In yet another example, the concentration of the highly absorbing element is higher in the absorbing layer than in the resist film.

[0098] The thickness of the absorber layer varies depending on the integration scheme. The resulting absorber layer can be very thin, ranging from 0.3 nm to 5 nm, because secondary electrons generated deeper than 5 nm are unlikely to penetrate the film and into the resist layer. However, any EUV absorber layer that can be etched with high etch selectivity to the photoresist film can also be applied thicker, and in some cases this may prove advantageous if an etch chemistry exists where it is possible to selectively remove the underlying device layer using the underlying film as an etch mask.

[0099] In one example, the absorbing layer is a metal oxide or a metal terminated with an alkyl group. The thin metal oxide or metal can be deposited by ALD or CVD. Examples include SnOx, BiOx, and Te. Following deposition, the film is MR x L yThe substrate may be capped with an alkyl-substituted precursor of the form: M is a metal, preferably with high EUV absorption, R is an alkyl or fluoroalkyl group, L is a ligand that reacts with the surface of a thin metal oxide or metal, x is an integer equal to or greater than 1, and y is an integer equal to or greater than 1. A back reactant can be used to better remove the ligand, and multiple cycles may be repeated to ensure complete saturation of the substrate surface. The surface is then ready for deposition of an EUV-sensitive resist film. One possible method is to produce a thin film of SnOx. Possible chemical reactions include growth of SnO2 by circulating a back reactant such as tetrakis(dimethylamino)tin and water or O2 plasma. After growth, a capping agent can be used. For example, it is possible to flow vapors of isopropyltris(dimethylamino)tin over the surface.

[0100] The absorbing layer can provide other functionality in addition to regulating the absorption of photons or radiation. In one example, the absorbing layer can be a photoresponsive adhesive layer that upon exposure to radiation can enhance adhesion to an overlying resist film. Prior to radiation exposure, the top surface of the absorbing layer can include unstable moieties that are cleavable under exposure to patterning radiation. Upon exposure, the unstable moieties can provide reactive centers that then participate in the formation of covalent bonds between the absorbing layer and the resist film. In this manner, the top surface of the absorbing layer can be characterized as a photoresponsive surface, and the absorbing layer itself can be characterized as a photoresponsive adhesive layer.

[0101] The advantages of the deposition of an absorber layer can be observed with any element that has a higher EUV cross-section than the substrate. Most used carbon-based underlayers have a relatively small EUV cross-section. Therefore, a wide variety of elements may be suitable for surface modification. Some particularly suitable elements are those that exhibit high EUV absorption cross-sections and can be effectively removed using dry etching processes, including In, Sn, Sb, Te, I, Pb, and Bi (see FIG. 1E). Alloys and oxides of these elements, as well as other compounds, may also be used.

[0102] Resist films and / or absorbing layers by being surface modified. One way to achieve surface modification is by using a reactant containing an EUV absorbing element. In some iterations, vapor of the reactant may be passed over the wafer. The wafer may be heated to provide thermal energy to drive the reaction. In some iterations, the heating may be 50-250°C. In some cases, pulses of reactant separated by pump and / or purging steps may be used. In some cases, a counter reactant may be pulsed between the reactant pulses, resulting in ALD or ALD-like growth. In other cases, both the reactant and counter reactant may be flowed simultaneously. Examples of elements useful for surface modification include I, F, Sn, Bi, Sb, Te, and oxides or alloys of these compounds.

[0103] Some examples of surface modification by this technique include evaporation / sublimation of either the pure elements or their sufficiently volatile compounds. Coatings may be applied by a variety of sputtering or physical vapor deposition techniques.

[0104] The modification process can leave the surface terminated with EUV labile groups such as alkyl groups (e.g., t-butyl, n-butyl, sec-butyl, i-propyl, etc.) or fluorine substituted alkyl groups, e.g., -CF3, -CF2CF3, etc. Such modifications can be provided on the surface of the substrate, the surface of the absorber layer, and / or the surface of the resist film.

[0105] Atomic layer deposition (ALD) techniques may also be advantageously used to controllably apply such thin films. In this manner, thin, highly EUV absorbing layers of tin, antimony, bismuth, and / or tellurium (such as, for example, tin telluride (SnTe), antimony telluride (SbTe), or bismuth telluride (BiTe) films) may be deposited using alternating flows of various volatile metal alkoxide-based precursors and Te-containing precursors (e.g., bis(trimethylsilyl)tellurium or any of those described herein). A non-limiting advantage of such processes is that the interface can be fine-tuned to maximize adhesion to inorganic metal oxide-based resist overlayers.

[0106] Another method that can be applied to achieve surface modification according to the present disclosure is by plasma techniques. A plasma can be irradiated so that reactive species in the plasma react with the surface to deposit highly EUV absorbing elements. The plasma can be a remote plasma or a direct plasma.

[0107] Some examples of these plasma techniques include plasma-deposited ashable carbon hardmask (AHM) films that are modified by exposure to plasma generated in a flow of iodine vapor (I2) in an inert carrier gas. Using I2 plasma, it is possible to break the C-C bonds of the surface and generate reactive I2 or atomic I species that can insert themselves to create CI functional groups on the surface. Such plasma strategies may be applicable to both diamond-like carbon films that contain primarily C-C single bonds, as well as materials that contain double bonds between carbon atoms. Alternatively, a thin iodine-rich layer can be grafted onto the surface by exposure to a plasma discharge generated in a flow of diiodomethane / He or other iodized hydrocarbons above the wafer surface.

[0108] Alternatively, thermal decomposition, chemical reaction decomposition, or plasma-induced decomposition of volatile organometallic precursors can be used to produce films with a predominantly elemental composition. For example, a thin tellurium-rich film can be deposited by thermal decomposition of bis(t-butyl)tellurium on an AHM carbon film heated to 250°C. Alternatively, an RF plasma can be ignited in a flow of bis(t-butyl)tellurium and H2 or He to deposit a tellurium-rich layer on the surface of the AHM film. Similarly, such a layer can be deposited by a chemical vapor deposition reaction between bis(trimethylsilyl)tellurium and water vapor. In yet another example, a thin Sn-rich film can be formed by generating a plasma in a mixture containing a tin precursor, such as tetrakis(dimethylamino)tin or tetra(isopropyl)tin, resulting in Sn-containing species bound to the surface by loss of one or more of the dimethylamino or isopropyl ligands.

[0109] The film or absorbing layer can include a capping layer. In one embodiment, the capping layer can provide a gradient film. One approach involves depositing a thin metallic Sn or Sn alloy based film on the surface of the substrate. Vapors of an alkyl organometallic tin precursor can be flowed into the chamber. The alkyl tin precursor can have the form SnR2 or SnR4 depending on the oxidation state of Sn. The alkyl group can be C n H 2n+1where n is typically 2 or greater. Examples include tetraisopropyltin, tetra(t-butyl)tin, and others described herein. The precursor vapor can be entrained in a suitable carrier gas (e.g., H2, He, Ar, or N2) and flowed into the chamber, and an RF plasma can be ignited between the wafer and the showerhead. As a result, a film is deposited that has a base composition similar to elemental Sn. The power of the plasma can be adjusted throughout the deposition, and possibly ramped down at the end. The plasma power is then turned off, but the alkyltin precursor still continues to flow. The result is a tin layer capped with alkyl groups. A resist, such as an organometallic resist, can then be deposited on top of the modified layer and introduced into an EUV scanner for exposure. Upon EUV exposure, the alkyl groups at the modified interface can undergo beta hydrogen elimination, resulting in the formation of Sn-H bonds at the interface. At this stage, or during a post-exposure bake, the Sn-H bonds can react with the resist to form Sn-O-Sn bridges across the interface, effectively enhancing adhesion of the film in the exposed areas.

[0110] Similar to the process described for alkyl-terminated Sn interface modification, organotellurium precursors can be used to deposit thin films of predominantly Te composition that provide high EUV absorptance. The organotellurium precursors may have the form R TeH or R2Te, where R is an alkyl group or a ligand molecule. The alkyl groups are C n H 2n+1n may be 0, n is 1, n is 2, n is 3 or more. Examples include hydride t-butyl tellurium, di(t-butyl) tellurium, di(isopropyl) tellurium, or bis(trimethylsilyl) tellurium. The diluent or carrier gas can include H2, He, Ar, or N2, and the plasma can be struck to deposit a thin Te-containing film. Ignition of the RF plasma deposits a primarily Te film. The power of the plasma can be adjusted throughout the deposition and finally turned down and extinguished while continuing to flow the organotellurium precursor, resulting in an alkyl group-capped Te underlayer. An EUV resist, such as the spin-on or dry-deposited metal organic resist described above, can then be deposited on top of the modified layer and introduced into an EUV scanner for exposure. Upon EUV exposure, the Te at the bottom of the film (e.g., deposited on the surface of the AHM carbon underlayer) strongly absorbs EUV photons that were not captured by the resist material, thereby maximizing the generation of secondary electrons that can induce cleavage of the alkyl groups and the formation of Te-Sn bonds at the interface. Alkyl groups present at the modified interface can undergo beta hydrogen elimination, resulting in the formation of reactive Te-H bonds at the interface. Upon baking, the Te-H can optionally react with Sn in the top resist film to form stable Sn-Te bonds. Optionally, these Te-H bonds can be converted to Te-OH bonds by the introduction of moisture.

[0111] In another example, enhanced EUV absorption can be achieved by incorporating F at the interface while also including OH, O, or COO groups to tune adhesion. xAbsorption in the EUV exposed regions can be enhanced by the presence of F from a polymer film) or from a fluorocarbon (or NF3, SF6, or other F source) plasma treatment of an organic (carbon-based) underlayer. In one example, a fluorocarbon-based film is deposited on top of a highly EUV absorbing film. In another example, a gas having fluorine, carbon, and optionally hydrogen can be flowed into the chamber to deposit a fluorocarbon-based film. Exemplary gases include, but are not limited to, CH2F2, C4F6, CHF3, CH3F, CF4, and C4F8. In some cases, an inert gas such as N2, Ar, or He, and optionally hydrogen, is also added to deposit CF x The plasma may be struck under selected conditions such that a layer is deposited on the wafer. CF x The chemistry and deposition conditions of the layer can be adjusted to be highly inert to certain gas phase chemistries.

[0112] In yet another example, thin CF x To form the terminal surface, an RF plasma can be generated in one or more fluorohydrocarbon precursors (examples include CH2F2, CF6, CHF3, CH3F, CF4, or CF8), optionally in combination with gases such as O2, H2, and / or CO2, to promote the formation of polar moieties to promote adhesion of the EUV-exposed metal oxide-based resist material to the substrate surface. The plasma is irradiated with CF under conditions shown to be effective in forming surface functional groups that are expected to enhance adhesion with the exposed organometallic film. x Conditions are selected such that a layer is deposited on the wafer. A resist (e.g., a dry-deposited metalorganic film) is then applied over the modified substrate surface and EUV patterned.

[0113] EUV exposure generates free F ions, which tend to form insoluble fluoride complexes that are more resistant to dissolution in photoresist developers. In other embodiments, F or CF are produced as a result of EUV-generated secondary electrons. xReactive sites can be formed on the surface through the abstraction of groups. The wafer can then be loaded into an ALD chamber where surface imaging can be performed. The ALD precursors may not be reactive with the unmodified fluorocarbon modified interface, but may nucleate on the exposed areas. Thus, an etch hard mask can be formed by this method and transferred to the underlayer, for example, as described in our prior application 62 / 767,198, which is incorporated herein by reference for its disclosure of surface imaging techniques.

[0114] Acid Method Any method that uses acid to develop or treat a resist film can treat any patterned structure or film herein.

[0115] 2A-2C illustrate methods where the patterning structure can include a homogenous resist film, a graded resist film, or a resist film with an absorbing layer. In particular, FIG. 2A illustrates a non-limiting method 200 using a patterning structure with a resist film 212. A non-limiting patterning structure can include a resist film 212 disposed on the top surface of a substrate 211. As can be seen, the resist film can include two different elements with high patterning radiation absorption cross-sections. In one embodiment, the elements include tin (Sn) and tellurium (Te). The resist film can include one or more other atoms provided by a reverse reactant, such atoms can include oxygen (O). The resist film can further include one or more ligands (R) that can be introduced by a precursor and can be characterized as labile EUV cleavable ligands. A patterning structure including such layers can be formed in any useful manner as described herein. In one embodiment, the resist film is a radiation sensitive resist film, an EUV sensitive film, or a photoresist layer.

[0116] In operation 201, a patterning structure is exposed to a patterned radiation exposure to provide an exposed film having non-radiation exposed regions 212a and radiation exposed regions 212b. Patterning can include the use of a mask having radiation transparent and radiation opaque regions as described herein.

[0117] In some embodiments, the EUV resist film contains metal atoms (M) and EUV labile ligands (R, e.g., alkyl groups) present on the surface in the EUV-exposed regions and can undergo beta hydrogen elimination such that the alkyl groups are removed leaving MH groups on the interface. These groups can be converted to M-OH groups upon exposure to oxygen and moisture. During exposure or a subsequent post-exposure bake step, some of these groups can react with hydroxyl groups already present in the film or hydroxyl groups generated by EUV-induced reactions in the resist film, creating strong bonds between the exposed resist film and the substrate. A post-exposure bake (PEB) can further strengthen adhesion and increase the number of crosslinking points. This difference in adhesion can aid in selectively removing unexposed areas as desired in negative resists. Spin-coated organic or organometallic resists can also benefit from a similar mechanism.

[0118] In operation 202, the exposed film is developed in the presence of an acid. Non-limiting acids include any of the acids described herein. As can be seen, development can selectively remove radiation unexposed regions 212a of the resist film 212 and retain radiation exposed regions 212b. Optionally, the exposed film can be baked before or after development, which can further increase the contrast in etch selectivity of the exposed film and / or enhance the hardness of the developed film. In other embodiments, the developed film is further exposed to a plasma-based etching process. In certain embodiments, the radiation unexposed regions are removed, thereby resulting in a negative resist. In other embodiments, the radiation exposed regions are removed, thereby resulting in a positive resist.

[0119] FIG. 2B illustrates a non-limiting method 220 using a patterning structure having a graded resist film 232. A non-limiting patterning structure can include a resist film 232 disposed on an upper surface of a substrate 231. As can be seen, the resist film can include two different elements having high patterning radiation absorption cross-sections, such elements being provided in a vertical gradient with a first concentration 232a of a first metal (here, a higher concentration of Te) adjacent to the substrate 231 and a second concentration 232b of the first metal (here, a lower concentration of Te) adjacent to the upper surface of the film. As can be further seen, the resist film can include one or more other atoms provided by a reverse reactant, such atoms can include oxygen (O) and can include one or more ligands (R), which can be introduced by a precursor and can be characterized as labile EUV cleavable ligands. A patterning structure including such layers can be formed in any useful manner as described herein. In one embodiment, the resist film is a radiation sensitive resist film, an EUV sensitive film, or a photoresist layer.

[0120] In operation 221, the patterning structure is exposed to a patterned radiation exposure to provide an exposed film having radiation non-exposed regions 233 a and radiation exposed regions 233 b. Patterning can include the use of a mask having radiation transparent and radiation opaque regions as described herein.

[0121] The presence of two different elements in the film may, in some cases, affect how the film is developed. For example, if one of the two elements is more resistant to etching or development, an additional development or treatment process may be required to remove the resist material. Furthermore, in some cases, even smaller amounts of the same element may be removed in a single development process. In other examples, development conditions may be optimized to remove both types of elements in the film. In a non-limiting embodiment, development in the presence of an acid and an oxygen-containing reagent (e.g., O2) can remove various types of elements in the film.

[0122] As seen in FIG. 2B, the exposed film may be developed in any useful manner to remove the desired regions. In operation 222, the exposed film is developed in the presence of an acid. Non-limiting acids include any of the acids described herein. As can be seen, development can selectively remove radiation-unexposed regions 233a of resist film 232 and retain radiation-exposed regions 233b. Optionally, the exposed film can be baked before or after development, which can further increase the contrast in etch selectivity of the exposed film and / or enhance the hardness of the developed film. In certain embodiments, the radiation-unexposed regions are removed, thereby resulting in a negative resist. In other embodiments, the radiation-exposed regions are removed, thereby resulting in a positive resist.

[0123] Alternatively, in operation 223, the exposed film is developed in any useful manner in the presence of an acid or other reagents and reactants described herein. As can be seen, the development selectively removes radiation unexposed regions 233a of the resist film 232, selectively retains radiation exposed regions 233b, and can result in residual species 233c present in any form (e.g., continuous or non-continuous layer). In certain embodiments, the residual species 233c includes an element present in high concentration in the initial resist layer 232. Here, the residual species 233c includes an increased concentration of Te. In operation 223, the development conditions can include conditions that effectively etch away Sn, but are less effective at removing Te. In this situation, the process can further include operation 224 configured to more effectively remove Te. As can be seen, in operation 224, the developed film is treated with an acid to remove the residual species 233c, thereby providing a pattern having radiation exposed regions 233b. After operation 224, the resulting film may be considered a treated film.

[0124] Optionally, the exposed film can be baked prior to development, which can further increase the contrast in etch selectivity of the exposed film. In some embodiments, the developed or treated film can be baked, which can further enhance hardness. In other embodiments, the developed or treated film is further exposed to a plasma-based etching process.

[0125] The present disclosure also encompasses any method of using a patterning structure having an absorbing layer, such as a method of making and / or using such a structure. In one embodiment, a method of making a patterning structure includes providing a substrate to receive a pattern, incorporating an absorbing layer on top of the substrate, and providing a resist film, where the absorbing layer is below the resist film and increases the radiation absorptivity and / or patterning performance of the resist film.

[0126] The absorber layer may include a highly absorbing element, which may be deposited by using one or more precursors (e.g., any of those described herein). The absorber layer may include primarily a highly absorbing element. In one embodiment, the absorber layer includes I, In, Sn, Bi, Sb, Te, or a combination thereof. In another embodiment, a single precursor is used. In yet another embodiment, two or more precursors are used. Optionally, the precursor is used with one or more counter reactants as described herein. The deposition may include, for example, ALD or CVD.

[0127] 2C illustrates a non-limiting method 240 of using a patterning structure having a radiation absorbing layer that can optionally act as a photoresponsive adhesive layer. The non-limiting patterning structure can include a substrate 251, a resist film 252, and an absorbing layer 253 below the resist film 252. A patterning structure including such layers can be formed in any useful manner as described herein. In an embodiment, the resist film is a radiation sensitive resist film, an EUV sensitive film, or a photoresist layer. In a particular embodiment, the absorbing layer includes any useful atom with a high radiation absorption cross section (e.g., I, Te, In, Sn, Sb, and / or Bi).

[0128] A radiation absorbing layer may be included to increase the absorptivity of the film, especially near the lower portion of the resist film. Optionally, the radiation absorbing layer may be photoresponsive. In this example, radiation may be used to pattern a photoresponsive surface of the absorbing layer 253, the photoresponsive surface having EUV labile ligands. As can be seen, the photoresponsive surface includes radiation unexposed regions 253a and radiation exposed regions 253b. In the radiation exposed regions 253b, adhesion between the resist film 252 and the absorbing layer 253 is enhanced. In certain embodiments, the enhanced adhesion reduces the required radiation dose, enabling desired patterned features to be provided in the resist film and / or the absorbing layer.

[0129] In operation 241, the patterning structure is exposed to a patterned radiation exposure to provide an exposed film having radiation non-exposed regions 252 a and radiation exposed regions 252 b. Patterning can include the use of a mask having radiation transparent and radiation opaque regions as described herein.

[0130] The surface of the absorbing layer can include a labile moiety such as halo, alkyl (e.g., branched alkyl), haloalkyl, or any of those described as R for formula (I) or (II) herein. As seen in FIG. 2C, a non-limiting absorbing layer includes Te having a labile moiety R', and a non-limiting resist film includes a tin oxide film having a labile moiety R. A non-limiting thickness of the absorbing layer is about 3-5 nm. In certain cases, the surface of the absorbing layer is treated with an organometallic precursor having a high absorbing element (e.g., Te) and a labile moiety (e.g., t-butyl). A non-limiting precursor including Te and t-butyl (t-Bu) can be (t-Bu)TeH or (t-Bu)2Te.

[0131] The unstable moieties R' can provide a passivated surface that can be activated (and thereby photoresponsive) upon exposure to radiation. In operation 241, the patterned structure is exposed to a patterned radiation exposure to provide an exposed film having radiation unexposed regions 252a and radiation exposed regions 252b in the resist film 252, and radiation unexposed regions 253a and radiation exposed regions 253b in the absorber layer 253. Upon radiation exposure, the unstable moieties R and R' are removed or cleaved, thus providing metal reaction centers, i.e., Sn in the resist film 252 and Te in the absorber layer 253, that can react to form intermetallic (MM) bonds (here, Sn-Te bonds). In the resist film, radiation-induced cleavage of Sn-R bonds in the organotin oxide layer also induces hardening and provides a more condensed metal oxide (tin oxide) network in the radiation-exposed regions.

[0132] As seen in the acts of FIG. 2C, in act 242, the exposed film is developed in the presence of an acid. Non-limiting acids include any of the acids described herein. As can be seen, development can selectively remove radiation unexposed regions 252a of resist film 252 while maintaining radiation exposed regions 252b. Such development can result in selective removal of portions of absorbing layer 253 in some cases. For example, development can selectively remove radiation unexposed regions 253a of absorbing layer 253 while maintaining radiation exposed regions 253b. Such development can include, for example, dry etching using any of the halide chemistries described herein, or plasma etching (e.g., using CH4 or F-based plasmas, including NF3, CF4, etc.).

[0133] Optionally, the exposed film can be baked before or after development, which can further increase the contrast in etch selectivity of the exposed film and / or enhance the hardness of the developed film. In certain embodiments, the areas not exposed to radiation are removed, thereby resulting in a negative resist. In other embodiments, the areas exposed to radiation are removed, thereby resulting in a positive resist.

[0134] Alternatively, in operation 243, the exposed film is developed in any useful manner in the presence of an acid or other reagents and reactants described herein. As can be seen, development can result in selective removal of radiation unexposed regions 252a of resist film 252 and selective retention of radiation exposed regions 252b, leaving remaining portions of absorbing layer 253a present. In certain embodiments, remaining portions of absorbing layer 253a include radiation unexposed regions and include a high concentration of a highly absorbing element (e.g., Te).

[0135] In operation 243, the development conditions may include conditions that effectively etch away a particular element (e.g., an element present in the resist film, such as Sn), but are less effective at removing another particular element (e.g., an element present in the absorber layer, such as Te). In this situation, the process may further include operation 244 configured to more effectively remove Te. As can be seen, in operation 244, the developed film is treated with acid to remove elements in the non-exposed regions 253a of the absorber layer, thereby providing a pattern having radiation-exposed regions 252b / 253b. After operation 244, the resulting film may be considered a processed film.

[0136] Optionally, the exposed film can be baked prior to development, which can further increase the contrast in etch selectivity of the exposed film. In some embodiments, the developed or treated film can be baked, which can further enhance hardness. In other embodiments, the developed or treated film is further exposed to a plasma-based etching process.

[0137] The methods herein may include optional additional steps before exposure, after development, and / or after treatment. In one example, the method may include providing a resist film. Such providing may include applying a resist film on a surface of a substrate, and optionally providing an absorbing layer between the resist film and the substrate. Applying the resist film or providing an absorbing layer may include delivering one or more precursors, reverse reactants, or other reactants to the substrate.

[0138] In one example, the resist film or absorber layer can include delivering a first precursor (having a highly absorbing first element), a second precursor (having a highly absorbing second element), and an optional reverse reactant. One non-limiting strategy includes the introduction of a first precursor containing Te and a second precursor containing Sn. As shown in FIG. 3A, the first precursor contains bis(trimethylsilyl) telluride (1) and the second precursor contains tetra(t-butoxy)tin (2), and deposition provides a network of SnTe material (3) with a trimethylsilyl surface, which can be further reacted (e.g., with a reverse reactant or alcohol) to remove the silyl groups. A layer containing such a network can be used as part of a resist layer and / or an absorber layer.

[0139] Another non-limiting strategy involves the introduction of an alternative (or additional) counter-reactant into the water to introduce an element with a much higher EUV absorption coefficient than oxygen. One example is the incorporation of Te, as shown in FIG. 3B. Bis(trimethyl)telluride (1) offers a viable option as a gas-phase co-reactant. In some embodiments, it can be combined with an alkyltin precursor, such as tris(t-butoxy)isopropyltin (4), and water. In this way, an EUV-reactive film can be produced with little reduction in reactive Sn-alkyl moieties (e.g., Sn-iPr moieties) near the bottom of the film. In the first part of the deposition, as shown in FIG. 3B, the co-reactant includes both water and bis(trimethyl)telluride (1). The initial film formed on the underlying substrate has significant amounts of both Sn and Te. As the deposition progresses, the ratio of bis(trimethyl)tellurium:tris(t-butoxy)isopropyltin decreases, which can result in the formation of a film that is relatively low in Te and relatively high in Sn compared to the initial part of the film. In various embodiments, the film may transition to a Te-free composition near the top surface of the film, for example to help minimize contamination and handling issues.

[0140] Another example could be the addition of different metals to the system to enhance absorption. For example, as shown in Figure 3C, a gradient film with bismuth and tin metal centers (8) can be synthesized using tris(dimethylamino)bismuth (6) and isopropyltris(dimethylamino)tin (7). The ratio of tris(dimethylamino)bismuth:isopropyltris(dimethylamino)tin in the precursor flow can be decreased as the film is deposited. This allows the bottom of the film to contain more bismuth metal centers than the top of the film. Closer to the top of the film, the gradient film can contain more tin centers (9), which can be synthesized using tris(dimethylamino)isopropyltin (7) and water, as shown in Figure 3D. Like Sn, Bi atoms exhibit extremely high EUV cross sections, but unlike Sn, they appear to have a lower tendency to condense into intractable binary metal oxides, even without bulky EUV-unstable substituents. Such films can be processed using wet (aqueous and non-aqueous) and / or dry (e.g., HCl or HBr-based, as described in International Application No. PCT / US2020 / 039615, entitled "PHOTORESIST DEVELOPMENT WITH HALIDE CHEMISTRIES," filed June 25, 2020, published as International Publication No. WO2020 / 264158, which is incorporated by reference herein for the purpose of describing applicable dry development techniques).

[0141] Various steps, operations, and apparatus for such patterning and developing steps include those useful in lithographic processes and any of those described herein. In one example, the lithographic process includes the use of extreme ultraviolet (EUV) lithography.

[0142] For example, Figure 4A illustrates an exemplary method 400 for providing a negative resist capable of removing EUV non-exposed regions. As can be seen, the method 400 includes depositing 401 a film 411 on an upper surface of a substrate 410. As described herein, the film includes an EUV sensitive material. In certain embodiments, the resist film 411 includes a gradient composition having a first concentration 411a near an upper portion of the film and a second concentration 411b near a lower portion of the film, where the first and second concentrations 411a / 411b are different (e.g., different in terms of concentration values, different atoms or elements, different ligands, etc.).

[0143] The method 400 may further include patterning the film with an EUV exposure 402. The EUV exposure may include, for example, an exposure having a wavelength in a range of about 10 nm to about 20 nm (e.g., about 13.5 nm in a vacuum atmosphere) in a vacuum atmosphere. The patterning may include the use of a mask 414 having EUV transparent and EUV opaque regions, where an EUV beam 415 is transmitted through the EUV transparent regions to the film 411. In this manner, the film includes EUV non-exposed regions 413a and EUV exposed regions 413b.

[0144] An additional step includes developing 403 the film with an acid, thereby selectively removing EUV non-exposed regions 413a and retaining EUV exposed regions 413b, and then providing a pattern or patterned film having removed regions 416a and retained regions 416b. The developing operation can include any of those described herein, including any of the acids described herein.

[0145] The method may include further steps of removing residual resist components. Accordingly, FIG. 4B illustrates an exemplary method 450 for providing a negative resist capable of removing EUV non-exposed regions. As can be seen, the method 450 includes depositing 451 a film 461 on an upper surface of a substrate 460. As described herein, the film includes an EUV sensitive material. In certain embodiments, the resist film 461 includes a gradient composition having a first concentration 461a near an upper portion of the film and a second concentration 461b near a lower portion of the film, the first and second concentrations 461a / 461b being different (e.g., different in terms of concentration values, different atoms or elements, different ligands, etc.).

[0146] The method 450 may further include patterning the film with EUV exposure 452. The patterning may include the use of a mask 464 having EUV transparent and EUV opaque regions, where an EUV beam 465 is transmitted through the EUV transparent regions to the film 461. In this manner, the film includes EUV non-exposed regions 463a and EUV exposed regions 463b.

[0147] An additional step includes developing 453 the film, thereby selectively removing EUV non-exposed regions 463a and retaining EUV exposed regions 463b, and then providing a patterned or patterned film having retained regions 466b. The developing operation can include any of those described herein, including any of the acids described herein. In some embodiments, the developing operation results in the formation of residual resist components 466a. In other embodiments, the method includes a stripping or treatment step that removes the residual resist components.

[0148] The method 450 can further include treating the developed film 454 with an acid. The treating can include exposing the developed film to any acid described herein, including dry or wet processes that include an acid. In this regard, the treated film can include the retained regions 467b and the removed regions 467a that are free of residual components.

[0149] The treatment and development steps may be performed under the same or different conditions, such as any of the conditions described herein for a development process (e.g., a dry development process and / or a wet development process). In one embodiment, both the stripping and development steps may include the use of an acid, which is a dry process. In another embodiment, stripping the resist layer includes the use of an acid in the gas phase and developing the film includes the use of a halide chemical acid in the liquid phase. Additional development process conditions are described herein.

[0150] Optionally (e.g., after development, before acid treatment, or after acid treatment), the method can further harden the exposed, developed, or patterned film (e.g., to provide a resist mask). The hardening step can include any useful process for further crosslinking or reacting the EUV non-exposed or EUV exposed regions. In an embodiment, hardening is performed to further crosslink or react the EUV exposed regions. Exemplary hardening steps can include exposure to plasma, annealing, thermal baking, or combinations thereof, which can be useful for a post-development bake (PDB) step. In certain embodiments, hardening can include exposure to plasma (e.g., O2, O3, Ar, He, or CO2 plasma), exposure to vacuum ultraviolet (VUV) radiation, optionally in the presence of an O2, Ar, He, or CO2 plasma environment, thermal annealing (e.g., at temperatures from about 180°C to about 240°C), optionally in the presence of an air ambient environment or atomic oxygen, or in the presence of an ozone / O2 ambient environment, or combinations thereof.

[0151] In one embodiment, the hardened or densified film is provided by annealing in the absence of oxygen (O)-containing gas. In some cases, annealing can include heating to a temperature of about 190° C. or higher. In some embodiments, annealing can be performed under vacuum, in the presence of an inert gas (e.g., nitrogen gas (N2), argon gas (Ar), or other non-oxidizing gas), or in the presence of an oxygen (O)-free gas, i.e., a gas free of oxygen atoms. Non-limiting examples of oxygen-free gas include O2-free gas or H2O-free gas. The inert gas can include one gas or a combination of inert gases. In some embodiments, the non-oxidizing gas is a gas having less than 1% oxygen (O)-containing gas (e.g., less than 1% O2 gas). The gas can be used at atmospheric pressure or below.

[0152] 5A shows a flowchart of an example method 500 having various operations, including optional operations. Optional steps may be performed to further condition, modify, or process the EUV sensitive film and / or substrate in any of the methods herein.

[0153] As can be seen, in operation 501, a film is deposited using one or more precursors with optional reverse reactants to provide photoresist (PR). In optional operation 502, the backside or bevel of the substrate may be cleaned and / or the edge bead of photoresist deposited in a previous step may be removed. Such cleaning or removal steps may be useful to remove particles that may be present after depositing a photoresist layer. The removal step may include treating the wafer with a wet metal oxide (MeOx) edge bead removal (EBR) step.

[0154] In optional operation 503, a post-apply bake (PAB) or another post-apply treatment can be performed. Such treatment can improve the etch resistance of the unexposed material to acid (in vapor or liquid form). In another example, a PAB operation is not performed because such treatment can reduce the hydrophobicity difference (or contrast) between the unexposed and exposed regions. In yet another example, the use of PAB removes residual moisture from the layer to form a hardened resist film. PAB involves some combination of thermal treatment, chemical exposure, and / or moisture that increases the EUV sensitivity of the film, thereby reducing the EUV dose to develop a pattern in the film. In certain embodiments, the PAB step is performed at a temperature greater than about 100° C., or between about 100° C. and about 200° C., or between about 100° C. and about 250° C. In other embodiments, the PAB step is performed at a temperature between about 190° C. and about 350° C. in the absence of an O-containing gas. In another example, the post-apply treatment includes exposing the film to an inert gas or CO2, which can optionally include cooling or heating. The use of an inert gas can provide metal-oxygen-metal species, and the use of CO2 can provide metal carbonate species within the film.

[0155] In operation 504, the film is exposed to EUV radiation to develop the pattern. Generally, the EUV exposure causes a change in the chemical composition of the film, resulting in a contrast in etch selectivity that can be used to remove portions of the film. Such contrast can provide a negative resist as described herein. The EUV exposure can include, for example, exposure having a wavelength in the range of about 10 nm to about 20 nm in a vacuum atmosphere (e.g., about 13.5 nm in a vacuum atmosphere).

[0156] Operation 505 is an optional post-exposure bake (PEB) of the exposed film to further remove residual moisture, promote chemical condensation within the film, or increase the contrast in the etch selectivity of the exposed film, or post-treat the film in any useful manner. In one example, no PEB operation is performed since such treatment may reduce the contrast between the unexposed and exposed regions. In another example, the exposed film may be thermally treated (e.g., optionally in the presence of various chemical species) to promote reactivity within the EUV exposed or non-EUV exposed portions of the resist upon exposure to a stripper or negative tone developer (e.g., a halogen-based acid such as HCl, HBr, HI, or combinations thereof in vapor or liquid form). In another example, the exposed film may be thermally treated to further crosslink ligands within the EUV exposed portions of the resist, thereby providing non-EUV exposed portions that can be selectively removed upon exposure to a stripper (e.g., a negative tone developer). In yet another example, the PEB is omitted.

[0157] The PR pattern can then be developed by negative tone development or negative tone development. In one example, the PR pattern is developed by negative development (e.g., as described herein). In various embodiments of development, the unexposed areas are removed (to provide a pattern in a negative tone resist). In other various embodiments of development, the exposed areas are removed (to provide a pattern in a positive tone resist). These steps can be dry processes (e.g., any of those described herein) or wet processes using one or more developers or developing solutions followed by an optional rinse (e.g., with deionized water or another solvent). In certain embodiments, the development step is a dry process applied to the tin-based film. In other embodiments, the development step is a wet process applied to the tin-based film.

[0158] In one example, operation 506 includes one or more dry processes using one or more developers that include an acid (e.g., acid vapor). In another example, operation 508 includes one or more wet processes using one or more developers that include an acid (e.g., acidic solution). The wet process may be optionally followed by an optional rinsing operation (e.g., with deionized water or another solvent) or an optional drying operation (e.g., with air or under inert conditions with optional heat). Optionally, the wet development may include or be followed by a prewetting step (e.g., by using an aqueous solvent such as any of those described herein), a rinsing step (e.g., by using an aqueous solvent such as any of those described herein), and / or a drying step. The acid development (with or without a rinsing operation) may be repeated n times, where n is 1, 2, 3, 4, 5, or more.

[0159] After development, one or more optional operations may be performed. For example, the method may include a treatment operation to remove residual species present after development. In one example, optional operation 507 includes treating the dry-developed PR pattern with a plasma-based process, a baking operation, or an acid-based treatment operation. In another example, optional operation 509 includes treating the wet-developed PR pattern with a plasma-based process, a baking operation, or an acid-based treatment operation. If a wet process is used, such a process may be followed by an optional rinsing operation (e.g., with deionized water or another solvent) or an optional drying operation (e.g., with air or under inert conditions with optional heat).

[0160] The method may include treating the photoresist pattern with an acid. Such a method may include developing, which may or may not include the same acid and / or the same conditions as the treatment operation. Figure 5B shows a flow chart of an exemplary method 510 having various operations, including optional operations. As can be seen, in operation 511, a film having a photoresist (PR) is deposited.

[0161] The method includes various optional operations described with respect to Figure 5A. Similarly, the example method 510 of Figure 5B can include optional operation 512 for cleaning the backside or bevel of the substrate and / or removing an edge bead of photoresist deposited in a previous step, optional operation 513 for PAB or another post-application treatment, and optional operation 515 for PEB or another post-exposure treatment.

[0162] In operation 514, the film is exposed to EUV radiation to develop the pattern. The PR pattern can then be developed by negative tone development or positive tone development. Operation 516 can be performed to dry develop the PR pattern, and operation 517 can be performed to treat the PR pattern with acid (e.g., to remove residual species present after development, and the acid can be provided in vapor or liquid form). Alternatively, operation 518 can be performed to wet develop the PR pattern, and operation 519 can be performed to treat the PR pattern with acid (e.g., to remove residual species present after development, and the acid can be provided in vapor or liquid form).

[0163] The PR film can be deposited in any useful manner. FIG. 5C shows a flow chart of an exemplary method 520 having various operations, including optional operations. As can be seen, in operation 521, a film and an absorber layer are deposited. In particular, operation 521a includes providing an absorber layer using a precursor (e.g., a first precursor different from that used in operation 521b) with an optional reverse reactant. Operation 521b includes providing a bulk photoresist (PR) using a precursor (e.g., a second precursor) with an optional reverse reactant.

[0164] The method further includes an optional operation 522 for cleaning the backside or bevel of the substrate and / or removing an edge bead of photoresist deposited in a previous step. Other optional operations include an operation 523 for a PAB or other post-application treatment, and / or an operation 525 for a PEB or other post-exposure treatment.

[0165] The film is exposed to EUV radiation to develop the pattern in operation 524. The PR pattern can then be developed by negative tone development or positive tone development.

[0166] The PR pattern can then be developed by negative or positive tone development. Operation 526 can be performed to dry develop the PR pattern with acid, and optional operation 527 can be performed to treat the PR pattern (e.g., to remove residual species present after development, the treatment may optionally include acid in vapor or liquid form). Alternatively, operation 528 can be performed to wet develop the PR pattern with acid, and optional operation 529 can be performed to treat the PR pattern (e.g., to remove residual species present after development, the treatment may optionally include acid in vapor or liquid form).

[0167] Dry processes may be used. In certain cases, only dry processes are used in the method. FIG. 5D shows a flow chart of an exemplary method 530 having various operations, including optional operations. As can be seen, in operation 531, a film and an absorber layer are deposited. In particular, operation 531a includes providing an absorber layer using a precursor (e.g., a first precursor different from that used in operation 531b) with an optional reverse reactant. Operation 531b includes providing a bulk photoresist (PR) using a precursor (e.g., a second precursor) with an optional reverse reactant.

[0168] Optional operations may include operation 532 for cleaning the backside or bevel of the substrate and / or removing an edge bead of photoresist deposited in a previous step, operation 533 for a PAB or another post-application treatment, and operation 535 for a PEB or another post-exposure treatment.

[0169] In operation 534, the film is exposed to EUV radiation to develop the pattern in a dry process. The PR pattern can then be dry developed by negative tone development or positive tone development. Operation 536 can be performed to dry develop the PR pattern with acid, and optional operation 537 can be performed to treat the PR pattern (e.g., to remove residual species present after dry development, where acid can optionally be provided in vapor form).

[0170] The post-development process may also include a dry process. Figure 5E shows a flow chart of an exemplary method 540 having various operations, including optional operations. As can be seen, in operation 541, a film and an absorber layer are deposited. In particular, operation 541a includes providing an absorber layer using a precursor (e.g., a first precursor different from that used in operation 541b) with an optional reverse reactant. Operation 541b includes providing a bulk photoresist (PR) using a precursor (e.g., a second precursor) with an optional reverse reactant.

[0171] Optional operations include operation 542 to clean the backside or bevel of the substrate and / or remove an edge bead of photoresist deposited in a previous step; operation 543 for PAB or another post-application treatment; and an operation 545 for PEB or other post-exposure processing.

[0172] In operation 544, the film is exposed to EUV radiation to develop the pattern in a dry process. The PR pattern can then be dry developed by negative tone development or positive tone development. Operation 546 can be performed to dry develop the PR pattern with an acid, and operation 547 can be performed to treat the PR pattern in a dry process. In particular, operation 547 can further include operation 547a of treating the PR pattern with an acid in vapor form (e.g., thereby providing a treated pattern) and operation 547b of treating the PR pattern with a plasma in the presence of a vapor (e.g., gas).

[0173] In some embodiments, the PAB and PEB may (or may not) be performed in a negative tone process. Without wishing to be limited by mechanism, the negative process described herein uses acid to remove resist components and also uses acid to remove residual resist components that may be present after development (e.g., dry development) and / or processing (e.g., acid processing). In certain embodiments, the residual resist components may include residual metal halide species or other residual species that include at least one highly absorbing element.

[0174] In any of the embodiments herein, the method can include rinsing, further hardening, and / or baking the patterned film (e.g., after development), thereby providing a resist mask disposed on top of the substrate. The hardening step can include any useful process for further crosslinking or reacting the EUV non-exposed or EUV exposed regions, such as exposing to a plasma (e.g., O2, O3, Ar, He, or CO2 plasma), exposing to ultraviolet radiation, annealing (e.g., at a temperature of about 180° C. to about 240° C.), thermal baking, or combinations thereof that can be useful for a post-development bake (PDB) step.

[0175] During the deposition, patterning, developing, and / or processing steps, any useful type of chemical can be used. Such steps can be based on dry processes using chemicals in the gas phase, or wet processes using chemicals in the wet phase. Various embodiments include combining film formation by gas phase deposition and dry operations by (EUV) lithography photopatterning with dry / wet development operations and optional dry / wet processing operations.

[0176] Thus, it has been demonstrated that high performance dry deposited EUV photoresist materials can be effectively patterned to give negative tone images or processed positive tone images. This also enables the application of acids, including dilute acids in vapor or liquid form, providing novel process flows with EUV PR films.

[0177] acid The acid can be provided as a vapor or as a liquid (e.g., with an optional solvent). The acid can include any useful acid, such as an inorganic acid, a halogen-containing acid, a hydrogen halide, an organic acid, a phosphorus oxoacid, a sulfur oxoacid, a carboxylic acid, or a silyl halide.

[0178] In some embodiments, the inorganic acid is an inorganic acid lacking a carbon atom. In one embodiment, the inorganic acid is a halogen-containing acid (e.g., hydrogen halide) containing fluorine, chlorine, bromine, and / or iodine, a phosphorus oxo acid, or a sulfur oxo acid. Non-limiting hydrogen halides include hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), and combinations thereof.

[0179] In some embodiments, the acid is a phosphorus oxoacid (eg, phosphoric acid), a sulfur oxoacid (eg, sulfuric acid), or a carboxylic acid (eg, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, citric acid, and combinations thereof).

[0180] In other embodiments, the acid is an organic acid or an organic halide compound. Non-limiting examples of organic acids include formic acid, acetic acid, trifluoroacetic acid, oxalic acid, citric acid, etc. Non-limiting examples of organic halide compounds include organic fluorine compounds, including trifluoroacetic acid, organic chlorine compounds, organic bromine compounds, or organic iodine compounds.

[0181] In certain embodiments, the acid may be provided by a reactant configured to provide an acid. Non-limiting reactants include borane halides including trichloroborane (BCl3), tribromoborane (BBr3), triiodoborane (BI3), silane halides including tetrachlorosilane (SiCl4), tetrabromosilane (SiBr4), tetraiodosilane (SiI4), trimethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl iodide, triethylsilyl chloride, triethylsilyl bromide, triethylsilyl iodide, tripropylsilyl chloride, tripropylsilyl bromide, tripropylsilyl iodide, triisopropylsilyl chloride ... propylsilyl, triisopropylsilyl bromide, triisopropylsilyl iodide, tributylsilyl chloride, tributylsilyl bromide, tributylsilyl iodide, triisobutylsilyl chloride, triisobutylsilyl bromide, triisobutylsilyl iodide, trisecbutylsilyl chloride, trisecbutylsilyl bromide, trisecbutylsilyl iodide, tritertbutylsilyl chloride, tritertbutylsilyl bromide, tritertbutylsilyl iodide, dimethyl-ethyl-silyl chloride, dimethyl-propyl-silyl chloride, dimethyl-iso Propyl-silyl, Dimethyl-butyl-silyl chloride, Dimethyl-isobutyl-silyl chloride, Dimethyl-sec-butyl-silyl chloride, Dimethyl-tert-butyl-silyl chloride, Dimethyl-tert-butyl-silyl bromide, Dimethyl-tert-butyl-silyl iodide, Methyl-diethyl-silyl chloride, Methyl-diethyl-silyl bromide, Methyl-diethyl-silyl iodide, Methyl-dipropyl-silyl chloride, Methyl-diisopropyl-silyl chloride, Methyl-dibutyl-silyl chloride, Methyl-diisobutyl-silyl chloride, Methyl-diseconyl chloride Trialkylsilyl halides including butyl-silyl, methyl-di-tert-butyl-silyl chloride, methyl-di-tert-butyl-silyl bromide, methyl-di-tert-butyl-silyl iodide, dimethyldichlorosilane, dimethyldibromosilane, dimethyldiiodosilane, diethyldichlorosilane, diethyldibromosilane, diethyldiiodosilane, dipropyldichlorosilane, dipropyldibromosilane, dipropyldiiodosilane, diisopropyldichlorosilane, diisopropyldibromosilane, diisopropyldiiodosilane,and dialkyldihalosilanes including dibutyldichlorosilane, dibutyldibromosilane, dibutyldiiodosilane, diisobutyldichlorosilane, diisobutyldibromosilane, diisobutyldiiodosilane, disecbutyldichlorosilane, disecbutyldibromosilane, disecbutyldiiodosilane, ditertbutyldichlorosilane, ditertbutyldibromosilane, ditertbutyldiiodosilane, methyl-ethyl-dichlorosilane, methyl-ethyl-dibromosilane, methyl-ethyl-diiodosilane, methyl-propyl-dichlorosilane, methyl-isopropyl-dichlorosilane, methyl-butyl-dichlorosilane, methyl-isobutyl-dichlorosilane, methyl-secbutyl-dichlorosilane, methyl-tertbutyl-dichlorosilane, methyl-tertbutyl-dibromidosilane, methyl-tertbutyl-diiodosilane, or combinations thereof. To form the acid, the borane halide may be provided in the presence of hydrogen gas (H2), a halide gas (e.g., chlorine gas (Cl2) or bromine gas (Br2)), or a hydrogen-containing reagent (e.g., a hydrogen halide such as HCl, HBr, or HI). In another embodiment, hydrogen gas (H2) and a halide gas (e.g., chlorine gas (Cl2) or bromine gas (Br2)) are combined to form the acid. In yet another embodiment, the silane halide may be provided in the presence of hydrogen gas (H2), a halide gas (e.g., chlorine gas (Cl2) or bromine gas (Br2)), or a hydrogen-containing reagent (e.g., a hydrogen halide such as HCl, HBr, or HI). Optionally, the acid may be provided by exposing the reactant to a plasma.

[0182] The acid can be used in a dry or wet process. In a dry process, the acid can be used in combination with the vapor of an oxygen-containing reagent. Non-limiting oxygen-containing reagents include oxygen gas (O2), ozone (O3), hydrogen peroxide (H2O2), and the like.

[0183] In a wet process, the acid can be provided with a solvent. Non-limiting solvents include aqueous solvents (e.g., water) or organic solvents, such as alcohols (e.g., isopropyl alcohol (IPA)), ketones (e.g., 2-heptanone, cyclohexanone, or acetone), ethers, such as glycol ethers (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA)), or esters (e.g., n-butyl acetate, gamma-butyrolactone, or ethyl 3-ethoxypropionate (EEP)), as well as combinations thereof. In other embodiments, the solvent comprises a combination of two or more different solvents.

[0184] Use of an acid can include any exposure time, such as from about 5 seconds to 3 minutes (e.g., from about 10 seconds to 60 seconds), which may be sufficient to allow development by removing unexposed areas or processing by removing residual species.

[0185] The aqueous acid can be provided in any useful concentration, including a concentration of about 0.01% (v / v) to 20% (v / v) of acid in a solvent (e.g., an aqueous solvent such as water). In other embodiments, the concentration is about 0.01% (v / v) to 2% (v / v), 0.01% (v / v) to 5% (v / v), or 0.01% (v / v) to 10% (v / v) of acid in the solvent.

[0186] Precursor The layers (e.g., absorber layers) and films (e.g., resist films) herein have a surface roughness of 1×10 7 cm 2 The resist film may include elements (e.g., metal or non-metal atoms including one, two, three, or more elements) having a high optical absorption cross section, such as 100 / mol or more. Such elements may be provided by depositing one or more precursors to provide the resist film.

[0187] In some embodiments, the film is a radiation sensitive film (e.g., an EUV sensitive film). This film can then act as an EUV resist, as further described herein. In certain embodiments, the layer or film can include one or more ligands (e.g., EUV labile ligands) that can be removed, cleaved, or crosslinked by radiation (e.g., EUV or DUV radiation).

[0188] The precursors can provide patternable films, patternable layers, and / or absorbing layers (or patterned radiation sensitive films, photopatternable films, radiation sensitive absorbing layers, photopatternable absorbing layers) that are sensitive to radiation. Such radiation can include EUV, DUV, or UV radiation provided by irradiating through a patterned mask, thereby resulting in patterned radiation. The films or absorbing layers themselves can be modified by exposure to such radiation to become radiation sensitive or photosensitive. In certain embodiments, the precursors are organometallic compounds that include at least one metal center.

[0189] The precursor can have any useful number and type of ligands. In some embodiments, the ligand can be characterized by its ability to react in the presence of a reverse reactant or in the presence of patterned radiation. For example, the precursor can include a ligand that reacts with a reverse reactant, which can introduce a linkage (e.g., an -O- linkage) between the metal centers. In another example, the precursor can include a ligand that leaves in the presence of patterned radiation. Such EUV labile ligands can include branched or straight chain alkyl groups with beta hydrogens, as well as any of those described herein for R in formula (I) or (II). In one embodiment, the precursor is a capping agent having two, three, or more hydrophobic ligands (e.g., organic ligands including optionally substituted alkyl, alkenyl, or alkynyl).

[0190] Other EUV labile ligands include alkyl, alkenyl, or alkynyl groups that may be branched or straight chain. Still other EUV labile ligands include aryl groups, such as aryl groups having one, two, or three rings. Such alkyl, alkenyl, alkynyl, and aryl groups may be substituted with one or more halo (e.g., one or more fluoro). Non-limiting labile ligands include optionally substituted C 1-12 Alkyl, optionally substituted C 2-12 Alkenyl, optionally substituted C 2-12 Alkynyl, optionally substituted C 1-12 Haloalkyl, optionally substituted C 2-12 Haloalkenyl, optionally substituted C 2-12 Included are haloalkynyl, optionally substituted aryl, or optionally substituted haloaryl.

[0191] The precursor can be any useful metal- or metalloid-containing precursor, such as an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In a non-limiting example, the precursor has the formula (I): M a R b (I)

[0023] The present invention includes a structure having the following structure: M is a metal or atom with a high EUV absorption cross section, R is independently H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, anionic ligand, neutral ligand, or multidentate ligand; a≧1, and b≧1.

[0192] In another non-limiting example, the precursor has formula (II): M a R b L c (II)

[0023] The present invention includes a structure having the following structure: M is a metal or atom with a high EUV absorption cross section, each R is independently halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is independently a ligand, anionic ligand, neutral ligand, polydentate ligand, ion, or other moiety that reacts with a reverse reactant; R and L together with M can optionally form a heterocyclyl group, or R and L together can optionally form a heterocyclyl group; a≧1, b≧1, and c≧1.

[0193] In some embodiments, each ligand in the precursor can be a ligand that reacts with a reverse reactant. In one example, the precursor comprises a structure having formula (II), where each R is independently L. In another example, the precursor comprises a structure having formula (IIa): M a L c (IIa)

[0023] The present invention includes a structure having the following structure: M is a metal or atom with a high EUV absorption cross section, each L is independently a ligand, ion, or other moiety that reacts with a reverse reactant; two L's together can optionally form a heterocyclyl group; a≧1, and c≧1. In certain embodiments of Formula (IIa), a is 1. In further embodiments, c is 2, 3, or 4.

[0194] For any formula herein, M is a high patterning radiation absorption cross section (e.g., 1×10 7 cm 2M may be a metal, metalloid, or atom having an EUV absorption cross section of 1000 .mu.m / mol or more. In some embodiments, M is tin (Sn), bismuth (Bi), tellurium (Te), cesium (Cs), antimony (Sb), indium (In), molybdenum (Mo), hafnium (Hf), iodine (I), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), platinum (Pt), and lead (Pb). In further embodiments, in formula (I), (II), or (IIa), M is Sn, a is 1, and c is 4. In other embodiments, in formula (I), (II), or (IIa), M is Sn, a is 1, and c is 2. In certain embodiments, M is Sn(II) (e.g., in formula (I), (II), or (IIa)), thereby providing a precursor that is a Sn(II)-based compound. In other embodiments, M is Sn(IV) (e.g., in formula (I), (II), or (IIa)), thereby providing a metal precursor that is a Sn(IV)-based compound. In certain embodiments, the precursor includes iodine (e.g., as in periodate).

[0195] For any formula herein, each R is independently H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy (e.g., -OR 1 , R 1 can be optionally substituted alkyl), optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, anionic ligands (e.g., oxide, chloride, hydride, acetate, iminodiacetate, propanoate, butanoate, benzoate, etc.), neutral ligands, or polydentate ligands.

[0196] In some embodiments, the optionally substituted amino is -NR 1 R 2 And each R 1 and R 2 are independently H or alkyl, or R 1 and R 2 taken together with the nitrogen atom to which each is attached, form a heterocyclyl group, as defined herein. In other embodiments, an optionally substituted bis(trialkylsilyl)amino is -N(SiR 1 R 2 R 3 )2, and each R 1 , R 2 , and R 3 is independently an optionally substituted alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR 1 R 2 R 3 And each R 1 , R 2 , and R 3 is independently optionally substituted alkyl.

[0197] In other embodiments, the formula is -NR 1 R 2 A first R (or a first L) and -NR 1 R 2 and each R 1 and R 2 are independently H or optionally substituted alkyl, or R from the first R (or first L) and R from the second R (or second L) 1 taken together with the nitrogen atom and metal atom to which each is attached, form a heterocyclyl group as defined herein. 1 The first R and -OR 1 and each R 1 is independently H or optionally substituted alkyl, or the first R through R 1 and R from the second R 1taken together with the oxygen atom and metal atom to which each is attached form a heterocyclyl group, as defined herein.

[0198] In some embodiments, at least one of R or L (e.g., in formula (I), (II), or (IIa)) is an optionally substituted alkyl. Non-limiting alkyl groups include C, where n is 1, 2, 3, or more, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. n H 2n+1 In various embodiments, R or L has at least one beta hydrogen, beta halogen, or beta fluorine. In other embodiments, at least one of R or L is a halo-substituted alkyl (e.g., a fluoro-substituted alkyl).

[0199] In some embodiments, each R or L, or at least one R or L (e.g., in formula (I), (II), or (IIa)) is halo. In particular, the precursor can be a metal halide. Non-limiting metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0200] In some embodiments, each R or L, or at least one of R or L (e.g., in formula (I), (II), or (IIa)) can include a nitrogen atom. In certain embodiments, one or more of R or L can be an optionally substituted amino, an optionally substituted monoalkylamino (e.g., -NR 1 H, R 1 is optionally substituted alkyl), optionally substituted dialkylamino (e.g., -NR 1 R 2 , each R 1 and R 2is independently an optionally substituted alkyl), or an optionally substituted bis(trialkylsilyl)amino. Non-limiting R and L substituents can include, for example, -NMe2, -NHMe, -NEt2, -NHEt, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)-(tbba), -N(SiMe3)2, and -N(SiEt3).

[0201] In some embodiments, each R or L, or at least one R or L (e.g., in formula (I), (II), or (IIa)) can include a silicon atom. In certain embodiments, one or more R or L can be an optionally substituted trialkylsilyl or an optionally substituted bis(trialkylsilyl)amino. Non-limiting R or L substituents can include, for example, -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2.

[0202] In some embodiments, each R or L, or at least one R or L (e.g., in formula (I), (II), or (IIa)) can include an oxygen atom. In certain embodiments, one or more R or L can be an optionally substituted alkoxy or an optionally substituted alkanoyloxy. Non-limiting R or L substituents include, for example, methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), acetate (-OC(O)-CH3), and -O=C(CH3)-CH=C(CH3)-O-(acac).

[0203] Any of the formulas herein may include one or more neutral ligands. Non-limiting neutral ligands include optionally substituted amines (e.g., NR or RN-Ak-NR, where each R can be independently H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl, and Ak is an optionally substituted alkylene), optionally substituted phosphines (e.g., PR or RP-Ak-PR, where each R can be independently H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl, and Ak is an optionally substituted alkylene), optionally substituted ethers (e.g., OR, where each R can be independently H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl), optionally substituted alkyl, optionally substituted alkene, optionally substituted alkyne, optionally substituted benzene, oxo, or carbon monoxide.

[0204] Any of the formulas herein may include one or more polydentate (e.g., bidentate) ligands. Non-limiting polydentate ligands include diketonates (e.g., acetylacetonate (acac) or -OC(R 1 )-Ak-(R 1 )CO- or -OC(R 1 )-C(R 2 )-(R 1 )CO-), bidentate dinitrogen chelates (e.g., -N(R 1 )-Ak-N(R 1 )-or-N(R 3 )-CR 4 -CR 2 =N(R 1 )-), aromatic (e.g., -Ar-), amidinate (e.g., -N(R 1 )-C(R 2 )-N(R 1 )-), aminoalkoxides (e.g., -N(R 1 )-Ak-O- or -N(R 1 )2-Ak-O-), diazadienyl (e.g., -N(R1 )-C(R 2 )-C(R 2 )-N(R 1 )-), cyclopentadienyl, pyrazolate, optionally substituted heterocyclyl, optionally substituted alkylene, or optionally substituted heteroalkylene. In certain embodiments, each R 1 is independently H, optionally substituted alkyl, optionally substituted haloalkyl, or optionally substituted aryl, and each R 2 is independently H or optionally substituted alkyl; R 3 and R 4 taken together form an optionally substituted heterocyclyl, Ak is optionally substituted alkylene, and Ar is optionally substituted arylene.

[0205] In certain embodiments, the precursor comprises tin. In some embodiments, the tin precursor comprises SnR or SnR2 or SnR4 or R3SnSnR3, where each R is independently H, halo, optionally substituted C 1-12 Alkyl, optionally substituted C 1-12 alkoxy, optionally substituted amino (e.g., -NR 1 R 2 ), optionally replaced by C 2-12 Alkenyl, optionally substituted C 2-12 Alkynyl, optionally substituted C 3-8 Cycloalkyl, optionally substituted aryl, cyclopentadienyl, optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR 1 R 2 R 3 )2), optionally substituted alkanoyloxy (e.g., acetate), diketonate (e.g., -OC(R 1 )-Ak-(R 2 )CO-), or bidentate dinitrogen chelates (e.g., -N(R 1 )-Ak-N(R 1 In certain embodiments, each R 1 , R2 , and R 3 are independently H or C 1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl), and Ak is an optionally substituted C 1-6 In certain embodiments, each R is independently selected from halo, optionally substituted C 1-12alkoxy, optionally substituted amino, optionally substituted aryl, cyclopentadienyl, or diketonate. 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), tri ...Me4), triphenyltin (SnMe4), triphenyltin (SnMe4), triphenyltin (SnMe4), triphenyltin (SnMe4), triphenyltin (SnMe4), triphenyltin (SnMe4), triphenyltin (SnMe4), triphenyltin (SnMe4), triphenyltin Trimethyl(phenyl)tin (SnMe3Ph), trimethyl(phenylethynyl)tin, tricyclohexyltin hydride, tributyltin hydride (SnBu3H), dibutyltin diacetate (SnBu2(CH3COO)2), tin(II) acetylacetonate (Sn(acac)2), tributyltin ethoxide (SnBu3(OEt), dibutyltin dimethoxide (SnBu2(OMe)2, tributyltin methoxide (SnBu3(OMe)), tin(I V) tert-butoxide (Sn(t-BuO)4), n-butyltin tributoxide (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)(N Sn(t-Bu)(NMe2)3, Sn(s-Bu)(NMe2)3, Sn(i-Bu)(NMe2)3, Sn(t-Bu)(NMe2)3, Sn(t-Bu)2(NMe2)2, Sn(t-Bu)(NEt2)3, Sn(tbba), Sn(II)(1,3-bis(1,1-dimethylethyl)-4,5-dimethyl-(4R,5R)-1,3,2-diazastanolidine-2-ylidene), or bis[bis(trimethylsilyl)amino]tin (Sn[N(SiMe3)2]2).

[0206] In other embodiments, the precursor comprises bismuth, such as BiR, where each R is independently halo, optionally substituted C1-12 Alkyl, mono-C 1-12 Alkylamino (e.g., -NR 1 H), Di-C 1-12 Alkylamino (e.g., -NR 1 R 2 ), optionally substituted aryl, optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR 1 R 2 R 3 )2), or diketonates (e.g., -OC(R 4 )-Ak-(R 5 In certain embodiments, each R 1 , R 2 , and R 3 is independently 1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl), and each R 4 and R 5 are independently H or optionally substituted C 1-12 and alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl).Non-limiting bismuth precursors include BiCl3, BiMe3, BiPh3, Bi(NMe2)3, Bi[N(SiMe3)2]3, and Bi(thd)3, where thd is 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0207] In other embodiments, the precursor comprises tellurium, such as TeR2 or TeR4, where each R is independently halo, optionally substituted C 1-12 Alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), optionally substituted C 1-12The tellurium precursor is an alkoxy, an optionally substituted aryl, a hydroxyl, an oxo, or an optionally substituted trialkylsilyl. Non-limiting tellurium precursors include dimethyltellurium (TeMe2), diethyltellurium (TeEt2), di(n-butyl)tellurium (Te(n-Bu)2), di(isopropyl)tellurium (Te(i-Pr)2), di(t-butyl)tellurium (Te(t-Bu)2), hydrogenated t-butyl tellurium (Te(t-Bu)(H)), Te(OEt)4, bis(trimethylsilyl)tellurium (Te(SiMe3)2), and bis(triethylsilyl)tellurium (Te(SiEt3)2).

[0208] The precursor can include antimony, such as SbR3, where each R is independently halo, optionally substituted C 1-12 Alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), optionally substituted C 1-12 alkoxy, or optionally substituted amino (e.g., -NR 1 R 2 , each R 1 and R 2 are independently H or optionally substituted C 1-12 Non-limiting antimony precursors include SbCl3, Sb(OEt)3, Sb(On-Bu)3, and Sb(NMe2)3.

[0209] Other precursors include indium precursors such as InR3, where each R is independently halo, optionally substituted C 1-12 Alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), or diketonate (e.g., -OC(R 4 )-Ak-(R 5 )CO-, each R 4 and R 5 are independently H or C 1-12Non-limiting indium precursors include InCp, where Cp is cyclopentadienyl, InCl, InMe, In(acac), In(CFCOCHCOCH), and In(thd).

[0210] The precursor can include iodine, such as RI, where R is iodine (I), hydrogen (H), optionally substituted C 1-12 Non-limiting iodine precursors include hydrogen iodide (HI), iodine gas (I2), diiodomethane (CH2I2), and periodate.

[0211] Further precursors and non-limiting substituents are described herein. For example, the precursor can be any of the structures of formula (I), (II), and (IIa) above, or formula (III), (IV), (V), (VI), (VII), or (VIII) described below. Any of the substituents M, R, X, or L described herein can be used in any of formulas (I), (II), (IIa), (III), (IV), (V), (VI), (VII), or (VIII).

[0212] The various atoms present in the precursors and / or reverse reactants can be delivered in a gradient film. In some embodiments of the techniques described herein, a non-limiting strategy that can further improve absorption in PR films is to form vertically graded films. Strategies to manipulate vertical composition gradients in PR films are particularly applicable to dry deposition methods such as CVD and ALD and can be achieved by adjusting the flow ratios between different precursors, reactants, reverse reactants, or gases during deposition. Types of composition gradients that can be manipulated include ratios between different R or L ligands for the precursors, use of different precursors with different M atoms, use of different precursors with different R ligands, use of different reverse reactants, and combinations of the above that can be modified or changed during deposition.

[0213] Such gradient films can be formed by using any of the precursors (e.g., tin or non-tin precursors) and / or reverse reactants described herein. Still other films, methods, precursors, and other compounds are described in U.S. Provisional Patent Application No. 62 / 909,430, filed October 2, 2019, and International Application No. PCT / US20 / 53856, filed October 1, 2020, published as International Publication No. WO2021 / 067632, each of which is entitled "SUBSTRATE SURFACE MODIFICATION WITH HIGH EUV ABSORBERS FOR HIGH PERFORMANCE EUV PHOTORESISTS," and in "PHOTORESIST WITH MULTIPLE PATTERNING RADIATION-ABSORBING ELEMENTS AND / OR VERTICAL COMPOSITIONS AND / OR ELECTRONIC COMPOSITIONS," filed June 24, 2020, published as International Publication No. WO2020 / 264557. No. PCT / US20 / 70172, entitled "METAL-CONTAINING FILMS THAT ARE SUBJECT TO LOW-TEMPERATURE GRADIENT," the disclosure of which pertains at least to the composition, deposition, and patterning of directly photopatternable metal-containing films to form EUV resist masks, is incorporated herein by reference.

[0214] The various atoms present in the precursor and / or reverse reactant can be provided in a capping layer, which is disposed on any useful layer or structure. The capping layer can be of any useful thickness (e.g., any thickness described herein, including from about 0.1 nm to about 5 nm).

[0215] Furthermore, two or more different precursors can be used within each layer (e.g., membrane or capping layer). For example, two or more of any metal-containing precursors herein can be used to form an alloy. In one non-limiting example, tin tellurides can be formed by using a tin precursor containing -NR2 ligands with RTaH, RTaD, or TeR2 precursors, where R is alkyl, particularly t-butyl or i-propyl. In another example, metal tellurides can be formed by using a first precursor containing an alkoxy or halo ligand (e.g., SbCl3) with a tellurium-containing precursor containing a trialkylsilyl ligand (e.g., bis(trimethylsilyl)tellurium).

[0216] Still other exemplary EUV-sensitive materials, as well as processing methods and apparatus, are described in U.S. Pat. No. 9,996,004, International Patent Publication No. WO2020 / 102085, and International Patent Publication No. WO2019 / 217749, each of which is incorporated by reference in its entirety herein.

[0217] As described herein, the films, layers, and methods herein can be used with any useful precursor. In some cases, the precursor has the following formula (III): MX n (III) and a metal halide having the formula: Depending on the selection of M, M is a metal, X is halo, and n is 2 to 4. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0218] Another non-limiting precursor is represented by formula (IV): MR n (IV)

[0023] The present invention includes a structure having the following structure: M is a metal and each R is independently H, optionally substituted alkyl, amino (e.g., -NR2, where each R is independently alkyl), optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR3), where each R is independently alkyl), or optionally substituted trialkylsilyl (e.g., -SiR3, where each R is independently alkyl), and depending on the selection of M, n is 2 to 4. Exemplary metals for M include Sn, Te, Bi, or Sb. The alkyl group can be C n H 2n+1 where n is 1, 2, 3, or more. Exemplary organometallic agents include SnMe4, SnEt4, TeR n , RTeR, t-butyl tellurium hydride (Te(t-Bu)(H)), dimethyltellurium (TeMe2), di(t-butyl)tellurium (Te(t-Bu)2), di(isopropyl)tellurium (Te(i-Pr)2), bis(trimethylsilyl)tellurium (Te(SiMe3)2), bis(triethylsilyl)tellurium (Te(SiEt3)2), tris(bis(trimethylsilyl)amido)bismuth (Bi[N(SiMe3)2]3), and Sb(NMe2)3.

[0219] Another non-limiting precursor is represented by the following formula (V): ML n (V) and a capping agent having the formula: M is a metal and each L is independently an optionally substituted alkyl, amino (e.g., -NR 1 R 2 , R 1 and R 2Each of may be H or alkyl as any described herein), alkoxy (e.g., -OR, where R is alkyl as any described herein), halo, or other organic substituents, and depending on the selection of M, n is 2-4. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary ligands include dialkylamino (e.g., dimethylamino, methylethylamino, and diethylamino), alkoxy (e.g., t-butoxy, and isopropoxy), halo (e.g., F, Cl, Br, and I), or other organic substituents (e.g., acetylacetone or N 2 ,N 3 -di-tertbutyl-butane-2,3-diamino). Non-limiting capping agents include SnCl4, SnI4, Sn(NR2)4, where each R is independently methyl or ethyl, or Sn(t-BuO)4. In some embodiments, multiple types of ligands are present.

[0220] The precursor has the following formula (VI): R n MX m (VI) and a hydrocarbyl substituted capping agent having the formula: M is a metal and R is a C with beta hydrogen 2-10R is alkyl or substituted alkyl, and X is a suitable leaving group for reaction with the hydroxyl group of the exposed hydroxyl group. In various embodiments, n=1-3, and m=4-n, 3-n, or 2-n, as long as m>0 (or m≧1). For example, R can be t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n-pentyl, n-hexyl, or derivatives thereof with a heteroatom substituent at the beta position. Suitable heteroatoms include halogen (F, Cl, Br, or I), or oxygen (-OH or -OR). X can be dialkylamino (e.g., dimethylamino, methylethylamino, or diethylamino), alkoxy (e.g., t-butoxy, isopropoxy), halo (e.g., F, Cl, Br, or I), or another organic ligand. Examples of hydrocarbyl substituted capping agents include t-butyltris(dimethylamino)tin (Sn(t-Bu)(NMe2)3), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe2)3), t-butyltris(diethylamino)tin (Sn(t-Bu)(NEt2)3), di(t-butyl)di(dimethylamino)tin (Sn(t-Bu)2(NMe2)2), sec-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe2)3), n-pentyl ... Examples of suitable tin ions include tris(dimethylamino)tin (Sn(n-pentyl)(NMe2)3), i-butyltris(dimethylamino)tin (Sn(i-Bu)(NMe2)3), i-propyltris(dimethylamino)tin (Sn(i-Pr)(NMe2)3), t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO)3), n-butyl(tris(t-butoxy)tin (Sn(n-Bu)(t-BuO)3), or isopropyltris(t-butoxy)tin (Sn(i-Pr)(t-BuO)3).

[0221] In various embodiments, the precursor comprises at least one alkyl group on each metal atom capable of undergoing a gas phase reaction, and other ligands or ions coordinated to the metal atom can be displaced by a counter reactant. Thus, another non-limiting precursor is represented by formula (VII): M a R b L c (VII) and an organometallic agent having the formula: M is a metal, R is an optionally substituted alkyl, L is a ligand, ion, or other moiety that reacts with a reverse reactant, and a > 1, b > 1, and c > 1. In certain embodiments, a = 1, and b + c = 4. In some embodiments, M is Sn, Te, Bi, or Sb. In certain embodiments, each L is independently an amino (e.g., -NR 1 R 2 , R 1 and R 2 Each of may be H or alkyl as described herein), alkoxy (e.g., -OR, where R is alkyl as described herein), or halo (e.g., F, Cl, Br, or I). Exemplary agents include SnMe3Cl, SnMe2Cl2, SnMeCl3, SnMe(NMe2)3, SnMe2(NMe2)2, SnMe3(NMe2), and the like.

[0222] In other embodiments, the non-limiting precursor has formula (VIII): M a L c (VIII) and an organometallic agent having the formula: M is a metal and L is a ligand, ion, or other moiety that reacts with the counter-reactant, where a > 1, and c > 1. In certain embodiments, c = n-1, and n is 2, 3, or 4. In some embodiments, M is Sn, Te, Bi, or Sb. The counter-reactant preferably has the ability to displace the reactive moiety ligand or ion (e.g., L in the formulas herein) so as to link at least two metal atoms via a chemical bond.

[0223] In any embodiment herein, R is optionally substituted alkyl (e.g., C 1-10In one embodiment, the alkyl can be substituted with one or more halo (e.g., halo-substituted C , including one, two, three, four, or more halo, such as F, Cl, Br, or I). 1-10 Exemplary R substituents include C alkyl, preferably with n≧3. n H 2n+1 , and C with 1≦x≦2n+1 n F x H( 2n+1-x In various embodiments, R has at least one beta hydrogen, beta halogen, or beta fluorine. For example, R may be selected from the group consisting of i-propyl, n-propyl, t-butyl, i-butyl, n-butyl, sec-butyl, n-pentyl, i-pentyl, t-pentyl, sec-pentyl, and mixtures thereof.

[0224] In any embodiment herein, L is an M-OH moiety, such as amino (e.g., -NR 1 R 2 , R 1 and R 2 may be any moiety that is readily displaced by a reverse reactant to produce a moiety selected from the group consisting of: alkyl (e.g., -OR, where R is alkyl as any of those described herein), alkoxy (e.g., -OR, where R is alkyl as any of those described herein), carboxylate, halo (e.g., F, Cl, Br, or I), and mixtures thereof.

[0225] The reverse reactant preferably has the ability to replace a reactive moiety, ligand, or ion (e.g., L in the formulas herein) to link at least two metal atoms via a chemical bond. Exemplary reverse reactants include oxygen-containing reverse reactants, such as oxygen (O2), ozone (O3), water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, dihydroxy alcohols, polyhydroxy alcohols, fluorinated dihydroxy alcohols, fluorinated polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, and combinations thereof. In various embodiments, the reverse reactant reacts with the precursor by forming an oxygen bridge between adjacent metal atoms. Other potential reverse reactants include hydrogen sulfide and hydrogen disulfide, which can bridge metal atoms via sulfur bridges, and bis(trimethylsilyl)tellurium, which can bridge metal atoms via tellurium bridges. In addition, hydrogen iodide may be utilized to incorporate iodine into the film.

[0226] Still other non-limiting reverse reactants include chalcogenide precursors having the formula ZR2, where Z is sulfur, selenium, or tellurium, and each R is independently H, optionally substituted alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc.), optionally substituted alkenyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or optionally substituted trialkylsilyl.

[0227] 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.

[0228] In some embodiments, the patterning structures include exposed hydroxyl groups or hydroxyl-terminated SnO x Without limiting the mechanism, function, or utility of the present technology, a surface layer or film comprising hydroxyl-terminated SnO x It is believed that the SnO layer can provide advantages such as improved adhesion of materials deposited on the surface of the substrate, and enhanced absorption of EUV (or other radiation) during patterning. Sensitivity and resolution to EUV or other radiation can vary depending on the thickness, density, and short-range charge transport properties of the SnO layer. x It may depend on the nature of the layer. In various embodiments, SnO x The layer has a thickness of 0.1 nm to 20 nm, or 0.2 nm to 10 nm, or 0.5 nm to 5 nm.

[0229] In some embodiments, hydroxyl-terminated SnO x The layer is deposited on the surface of the substrate by vapor deposition. In such a method, the deposition is nwith an oxygen-containing reverse reactant, where X is a ligand such as dialkylamino (e.g., dimethylamino, methylethylamino, and diethylamino), alcohol (e.g., t-butoxy and isopropoxy), halogen (e.g., F, Cl, Br, and I), or other organic substituents (e.g., acetylacetone, N2,N3-di-tertbutyl-butane-2,3-diamino). For example, Sn-X n may be SnCl4, SnI4, or Sn(NR2)4, where R is methyl or ethyl, or Sn(t-BuO)4. In some embodiments, there are multiple types of ligands. The oxygen-containing reverse reactant may be selected from the group consisting of water, hydrogen peroxide, formic acid, alcohol, oxygen, ozone, and combinations thereof.

[0230] Suitable vapor deposition processes include chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma enhanced chemical vapor deposition (PECVD), or plasma enhanced atomic layer deposition (PEALD). In some embodiments, the deposition is n In some embodiments, the deposition is an ALD process in which a Sn-X n and an oxygen-containing counter reactant are simultaneously flowed. x Materials and processes useful herein for depositing layers are described in Nazarov et al., Atomic Layer Deposition of Tin Dioxide Nanofilms: A Review, 40 Rev. Adv. Mater. Sci. 262 (2015). x The substrate may be deposited by a CVD or ALD process, as described herein.

[0231] A surface activation operation can be used to activate the surface for future operations. For example, SiO xFor surfaces, water or oxygen / hydrogen plasma can be used to form hydroxyl groups on the surface. For carbon- or hydrocarbon-based surfaces, water, hydrogen / oxygen, or CO2 plasma, or ozone treatment can be used to form carboxylic acid and / or hydroxyl groups. Such approaches can improve adhesion of resist features to the substrate, which in some cases may peel or lift off in the solvent used for development.

[0232] Adhesion can also be enhanced by inducing roughness in the surface to increase the surface area available for interaction and to directly improve mechanical adhesion. For example, a sputtering process using Ar or other non-reactive ion bombardment can be used first to result in a rough surface. The surface can then be terminated with the desired surface functional groups (e.g., hydroxyl and / or carboxylic acid groups) as described above. On carbon, a combination approach can be used in which a chemically reactive oxygen-containing plasma such as CO2, O2, H2O (or a mixture of H2 and O2) can be used to etch away a thin layer of the film with localized inhomogeneities and simultaneously terminate with -OH, -OOH, or -COOH groups. This approach can be performed with or without bias. In conjunction with the surface modification strategies described above, this approach can serve the dual purpose of roughening and chemical activation of the substrate surface for direct adhesion to inorganic metal oxide-based resists or as an intermediate surface modification for further functionalization.

[0233] The patterning structure can include any useful substrate. For example, a next wafer can be prepared having a substrate surface of the desired material, with the top material being the layer to which the resist pattern is transferred. The choice of material can vary depending on the integration, but it is generally desirable to select a material that can be etched with high selectivity to (i.e., much faster than) the EUV resist or resist film. In some embodiments, the substrate is a hard mask used in the lithographic etching of the underlying semiconductor material. Hard masks can be made of amorphous carbon (aC), tin oxide (e.g., SnO x ), silicon oxide (e.g., SiO x ), silicon oxynitrides (e.g., SiO x N y ), silicon oxycarbide (e.g., SiO x C y ), silicon nitride (e.g., Si3N4), titanium oxide (e.g., TiO2), titanium nitride (e.g., TiN), tungsten (e.g., W), doped carbon (e.g., W-doped C), tungsten oxide (e.g., WO x ), hafnium oxide (e.g., HfO2), zirconium oxide (e.g., ZrO2), and aluminum oxide (e.g., Al2O3). Suitable substrate materials include various carbon-based films (e.g., ashable hardmasks (AHMs), silicon-based films (e.g., SiO x , SiC x , SiO x C y , SiO x N y , SiO x C y N z ), a-Si:H, poly-Si, or SiN), or any other (generally sacrificial) film applied to facilitate the patterning process. For example, the substrate is preferably a SnO x In various embodiments, the layer may be from 1 nm to 100 nm thick, or from 2 nm to 10 nm thick.

[0234] If there are device features present on the substrate to be patterned that form significant topography, another important function of the underlayer is to be able to overcoat and planarize the existing topography, so that subsequent patterning steps can be performed on a flat surface with all areas of the pattern in focus. In such applications, the underlayer (or at least one of the underlayers) is typically applied using spin-coating techniques. If the photoresist material used has a significant inorganic component, e.g., exhibits a predominantly metal oxide skeleton, the underlayer may advantageously be a carbon-based film applied by either spin-coating or a dry vacuum-based deposition process. The layers may include various AHM films with carbon-based and hydrogen-based compositions, and may be doped with additional elements such as tungsten, boron, nitrogen, or fluorine.

[0235] In various embodiments, the surface (e.g., of a substrate and / or film) includes exposed hydroxyl groups on its surface. In general, the surface can be any surface that includes or has been treated to provide an exposed hydroxyl surface. Such hydroxyl groups can be formed on the surface by surface treatment of the substrate using oxygen plasma, water plasma, or ozone. In other embodiments, the surface of the film can be treated to provide exposed hydroxyl groups, over which a capping layer can be applied. In various embodiments, the hydroxyl-terminated metal oxide layer has a thickness of 0.1 nm to 20 nm, or 0.2 nm to 10 nm, or 0.5 nm to 5 nm.

[0236] The embodiments disclosed herein describe the deposition of materials onto a substrate, such as a wafer, substrate, or other workpiece. The workpiece may be of various shapes, sizes, and materials. In this application, the terms "semiconductor wafer," "wafer," "substrate," "wafer substrate," and "partially fabricated integrated circuit" are used interchangeably. Those skilled in the art will appreciate that the term "partially fabricated integrated circuit" may refer to a silicon wafer during any of the many stages of integrated circuit fabrication. Wafers or substrates used in the semiconductor device industry have diameters of approximately 200 mm, or 300 mm, or 450 mm. Unless otherwise stated, the process details recited herein (e.g., flow rates, power levels, etc.) relate to the processing of 300 mm diameter substrates, or processing chambers configured to process 300 mm diameter substrates, and may be appropriately scaled for other sized substrates or chambers. In addition to semiconductor wafers, other workpieces that may be used in the embodiments disclosed herein include various articles, such as printed circuit boards. The processes and apparatus may be used in the fabrication of semiconductor devices, displays, and the like.

[0237] Lithography Process Patterning of thin films in semiconductor processing is often a step in the fabrication of semiconductors. Patterning involves lithography. In photolithography, such as 193 nm photolithography, a pattern is printed by emitting photons from a photon source onto a mask and printing the pattern onto a light-sensitive photoresist, which triggers a chemical reaction in the photoresist that, after development, removes certain portions of the photoresist to form the pattern.

[0238] Advanced technology nodes (as defined by the International Technology Roadmap for Semiconductors) include the 22 nm, 16 nm, and beyond. For example, at the 16 nm node, the width of a via or line in a damascene structure is approximately 30 nm or less. The scaling of features on advanced semiconductor integrated circuits (ICs) and other devices is driving lithography to improve resolution.

[0239] Extreme ultraviolet (EUV) lithography can extend lithography techniques by moving to shorter imaging source wavelengths than can be achieved with photolithography methods. EUV sources with wavelengths of about 10-20 nm, or 11-14 nm, for example 13.5 nm, can be used for state-of-the-art lithography tools, also called scanners. EUV radiation is strongly absorbed by a wide range of solid and fluid materials, including quartz and water vapor, and therefore operates in a vacuum.

[0240] Conventional organic chemically amplified resists (CARs) have several drawbacks when used in EUV lithography, such as low absorption coefficients and acid diffusion of photoactivated species, especially in the EUV region. To overcome the low absorption coefficient, a relatively thick CAR film is required, but there is a risk of pattern collapse. In addition, the wide clearing radius during the acid diffusion process results in relatively high line roughness in the patterned CAR film. Quenchers can be used to reduce the acid diffusion radius, but at the cost of reduced sensitivity. Therefore, the lithographic performance of current CARs generally cannot achieve the desired EUV lithographic performance.

[0241] Directly photopatternable EUV resists containing metals and / or metal oxides mixed within the organic component are promising in that they can enhance the absorption of EUV photons, generate secondary electrons, and / or exhibit increased etch selectivity relative to the underlying film stack and device layers. Spin-on organometallic resists available from Inpria Corp. (Corvallis, Oregon) have substantially higher absorption coefficients than CAR and can be made significantly thinner while providing good etch resistance. Spin-on formulations generally result in spatially homogeneous films.

[0242] Dry deposition of metalorganic-based photopatternable EUV resists has also been described, for example, in Applicant's prior International Application No. PCT / US19 / 31618, entitled "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS," published as International Publication No. WO2019 / 217749, filed May 9, 2019, the above disclosure relating to the composition, dry deposition, and patterning of directly photopatternable metalorganic-based metal oxide films to form EUV resist masks, is incorporated herein by reference.

[0243] In most or all of these organometallic-based resists, all other elements except the metal center have low EUV absorption cross sections. Other highly EUV absorbing elements could be introduced into the resist as part of an alternative metal center or reverse reactant, or by replacing hydrogen on the organic group with fluorine or iodine, which could further increase the EUV absorption in the PR and thus further reduce the EUV dose required for patterning, and these possibilities have been explored in the applicant's previous work.

[0244] Further improvements in the performance of EUV lithography organometallic resists are contemplated by increasing sensitivity, reducing line edge roughness, and / or improving resolution, captured in a term referred to herein as "Z-factor." This disclosure outlines methods to improve the sensitivity of these resists by addressing the underlayers of the organometallic resist film and incorporating highly EUV absorbing elements below the photoactive layer of the film to increase the EUV absorptivity and patterning performance of the EUV photoresist. The compositions, structures, and methods described may be applicable to both dry-deposited organometallic photoresist strategies, as well as CAR and spin-on organometallic films.

[0245] EUV lithography utilizes an EUV resist, which can be a polymer-based chemically amplified resist delivered by liquid-based spin-on techniques, or a metal oxide-based resist delivered by dry vapor deposition techniques. Such an EUV resist can include any EUV-sensitive film or material described herein. Lithography methods can include, for example, patterning the resist by exposing the EUV resist to EUV radiation to form a photopattern, and subsequently developing the pattern by removing portions of the resist according to the photopattern to form a mask.

[0246] It should also be understood that the present disclosure relates to lithographic patterning techniques and materials exemplified by EUV lithography, but is also applicable to other next-generation lithography techniques. In addition to EUV, which includes the standard 13.5 nm EUV wavelength currently in use and under development, the most relevant radiation sources for such lithography are DUV (deep UV), which generally refers to the use of 248 nm or 193 nm excimer laser sources, X-ray, which formally includes EUV at the lower energy range of the X-ray range, and e-beam, which can cover a wide energy range. Such methods include contacting a substrate (e.g., optionally having exposed hydroxyl groups) with a precursor (e.g., any of those described herein) to form a metal oxide (e.g., a layer including a network of metal oxide bonds, which may include other non-metallic and non-oxygen groups) film as an imaging / PR layer on the surface of the substrate. The specific method may depend on the particular materials and applications used in the semiconductor substrate and the final semiconductor device. Thus, the methods described in this application are merely exemplary of methods and materials that can be used with current technology. In some embodiments, lithography involves the use of a radiation source having a wavelength between 10 nm and 400 nm.

[0247] Directly photopatternable EUV resists may be composed of or include metals and / or metal oxides. Metals / metal oxides are very promising in that they can enhance EUV photon absorption, generate secondary electrons, and / or exhibit increased etch selectivity relative to the underlying film stack and device layers. Additional processes used during lithography are described in more detail below.

[0248] Deposition processes including dry or wet deposition As mentioned above, the present disclosure provides methods for films on semiconductor substrates that can be patterned using EUV or other next generation lithography techniques. Methods include methods in which a polymerized organometallic material is generated in vapor and deposited on a substrate. In some embodiments, dry deposition can use any useful precursor (e.g., metal halides, capping agents, or organometallic agents described herein). In other embodiments, spin-on formulations can be used. The deposition process can include applying the EUV-sensitive material as a resist film or an EUV-sensitive film.

[0249] Such EUV-sensitive films include materials that undergo changes upon exposure to EUV, such as loss of bulky pendant ligands attached to metal atoms. EUV-induced cleavage can provide intermediates that are retained by use of a negative tone developer, while the exposed regions can be further processed to provide materials rich in dense MOMs.

[0250] EUV patterning creates regions of the film with altered physical or chemical properties compared to unexposed regions. These properties can be exploited in subsequent processing, such as dissolving either the unexposed or exposed regions, or selectively depositing material in either the exposed or unexposed regions. In some embodiments, the unexposed film has a hydrophobic surface and the exposed film has a hydrophilic surface under the conditions under which such subsequent processing is carried out (it is recognized that the hydrophilic nature of the exposed and unexposed regions is interrelated). For example, material removal can be achieved by exploiting differences in the chemical composition, density, and crosslinking of the film. Removal can be by wet or dry processing, as further described herein.

[0251] The thickness of the EUV patternable film formed on the surface of the substrate may vary according to the surface characteristics, the materials used, and the processing conditions. In various embodiments, the film thickness may range from about 0.5 nm to about 100 nm. Preferably, the film has a thickness sufficient to absorb a majority of the EUV light under the conditions of EUV patterning. For example, the overall absorption of the resist film may be 70% or less (e.g., 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5% or less) such that the resist material at the bottom of the resist film is fully exposed. In some embodiments, the film thickness is 10 nm to 20 nm. Without limiting the mechanism, function, or utility of the present disclosure, it is believed that the process of the present disclosure has beneficial surface adhesion properties of the substrate and can be applied to a wide variety of substrates. Furthermore, as described herein, the deposited film can closely conform to surface features, providing advantages in forming a mask over a substrate, such as a substrate having underlying features, without "filling" or planarizing such features.

[0252] The film may be comprised of a metal oxide layer deposited in any useful manner. Such a metal oxide layer may be deposited or applied by using any EUV-sensitive material described herein, such as a precursor (e.g., a metal-containing precursor, a metal halide, a capping agent, or an organometallic agent) in combination with a reverse reactant. In an exemplary process, a polymerized organometallic material is formed in the gas phase or in situ on the surface of a substrate to provide a metal oxide layer. The metal oxide layer may be used as a film, an adhesion layer, or a capping layer.

[0253] Optionally, the metal oxide layer can include a hydroxyl-terminated metal oxide layer, which can be deposited by using a capping agent (e.g., any described herein) with an oxygen-containing reverse reactant. Such a hydroxyl-terminated metal oxide layer can be used as an adhesion layer between two other layers, such as, for example, between a substrate and a film and / or between a photoresist layer and a capping layer.

[0254] Exemplary deposition techniques (e.g., for films) include any described herein, such as ALD (e.g., thermal ALD and plasma-enhanced ALD), spin-coat deposition, PVD including PVD co-sputtering, CVD (e.g., PE-CVD or LP-CVD), sputter deposition, e-beam deposition including e-beam co-evaporation, or the like, or combinations thereof, such as ALD with a CVD component, discontinuous ALD-like processes, such as where precursors and counter-reactants are separated in either time or space.

[0255] Further description of precursors and methods for their deposition as EUV photoresist films applicable to the present disclosure can be found in International Application No. PCT / US19 / 31618, entitled "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS," published as International Publication No. WO2019 / 217749, filed May 9, 2019. The thin films can include optional materials in addition to the precursors and back reactants to modify the chemical or physical properties of the film, such as modifying the film's sensitivity to EUV or enhancing etch resistance. Such optional materials may be introduced, such as by doping, before deposition on the substrate, during deposition on the substrate, and / or during vapor phase formation after deposition of the film. In some embodiments, a mild remote H2 plasma can be introduced to, for example, replace some Sn-L bonds with Sn-H, which can increase the reactivity of the resist under EUV. In other embodiments, CO2 can be introduced to replace some Sn-O bonds with Sn-CO3 bonds, which can make them more resistant to dry or wet development.

[0256] In general, the method can include mixing a vapor flow of a precursor (e.g., a metal-containing precursor such as an organometallic agent) with an optional vapor flow of a reverse reactant to form a polymerized organometallic material, and depositing the organometallic material onto a surface of a semiconductor substrate. In some embodiments, the precursor and the optional reverse reactant can be mixed to form a polymerized organometallic material. As will be appreciated by those skilled in the art, the mixing and deposition aspects of the process can be simultaneous in a substantially continuous process.

[0257] In an exemplary sequential CVD process, two or more gas streams of precursors and optional reverse reactants are introduced in separate inlet paths into a deposition chamber of a CVD apparatus where they mix and react in the gas phase to form a coagulated polymeric material or film on a substrate (e.g., via metal-oxygen-metal bond formation). The gas streams can be introduced, for example, using separate injection inlets or a dual plenum showerhead. The apparatus is configured such that the flows of precursors and optional reverse reactants are mixed in the chamber, thereby allowing the precursors and optional reverse reactants to react and form a polymerized organometallic material or film (e.g., a metal oxide coating or a coagulated polymeric material via metal-oxygen-metal bond formation, etc.).

[0258] To deposit metal oxides, the CVD process is typically carried out at reduced pressure, such as between 0.1 Torr and 10 Torr. In some embodiments, the process is carried out at a pressure between 1 Torr and 2 Torr. The temperature of the substrate is preferably lower than the temperature of the reactant stream. For example, the substrate temperature can be between 0° C. and 250° C., or between ambient temperature (e.g., 23° C.) and 150° C.

[0259] To deposit the coagulated polymeric material, the CVD process is generally carried out at reduced pressures, such as 10 mTorr to 10 Torr. In some embodiments, the process is carried out at 0.5 to 2 Torr. The temperature of the substrate is preferably at or below the temperature of the reactant stream. For example, the substrate temperature can be from 0° C. to 250° C., or from ambient temperature (e.g., 23° C.) to 150° C. In various processes, deposition of the polymerized organometallic material onto the substrate occurs at a rate inversely proportional to the surface temperature. Without limiting the mechanism, function, or utility of the present technology, it is believed that the products from such gas-phase reactions become heavier in molecular weight as the metal atoms are crosslinked by the counter reactant, and are then condensed or, in some cases, deposited onto the substrate. In various embodiments, the steric hindrance of the bulky alkyl groups further prevents the formation of a densely packed network, resulting in a low-density film with increased porosity.

[0260] Using dry deposition techniques, it is possible to adjust the composition of the film as it grows. In a CVD process, this can be accomplished by altering the relative flows of the first and second precursors during deposition. Deposition can be performed at temperatures between 30°C and 200°C, and at pressures between 0.01 Torr and 100 Torr, more commonly around 0.1 Torr to 10 Torr.

[0261] Films (e.g., metal oxide coatings or aggregated polymeric materials, such as via metal-oxygen-metal bond formation) can also be deposited by ALD processes. For example, precursors and optional counter reactants are introduced at separate times that represent ALD cycles. The precursors react on the surface to form up to a monolayer of material at a time in each cycle. This can allow for excellent control over the uniformity of film thickness across the surface. ALD processes are generally performed at reduced pressures, such as 0.1 Torr to 10 Torr. In some embodiments, the process is performed at 1 Torr to 2 Torr. The substrate temperature can be from 0° C. to 250° C., or from ambient temperature (e.g., 23° C.) to 150° C. The process can be a thermal process, or preferably, a plasma-assisted deposition.

[0262] Any of the deposition methods herein can be modified to allow the use of two or more different precursors. In one embodiment, the precursors can contain the same metal but different ligands. In another embodiment, the precursors can contain different metal groups. In one non-limiting example, alternating flows of various volatile precursors can provide mixed metal-containing layers, such as using a metal alkoxide precursor with a first metal (e.g., Sn) and a silyl-based precursor with a different second metal (e.g., Te).

[0263] The processes herein can be used to achieve surface modification. In some iterations, vapors of the precursors can be passed over the wafer. The wafer can be heated to provide thermal energy for the reaction to proceed. In some iterations, the heating can be from about 50°C to about 250°C. In some cases, pulses of precursors separated by pump and / or purging steps can be used. For example, a first precursor can be pulsed between pulses of a second precursor pulse, resulting in ALD or ALD-like growth. In other cases, both precursors 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.

[0264] The processes herein can be used to deposit thin metal oxides or metals by ALD or CVD. Examples include tin oxide (SnOx), bismuth oxide (BiOx), and Te. Following deposition, the films can be modified to form M films as described elsewhere herein. a R b L cThe surface may be capped with an alkyl-substituted precursor in the form of . A back reactant can be used to better remove the ligands, and multiple cycles can be repeated to ensure complete saturation of the substrate surface. The surface is then ready for deposition of an EUV-sensitive film. One possible method is to generate a thin film of SnOx. Possible chemistries include growth of SnO2 by circulating a back reactant such as tetrakis(dimethylamino)tin and water or O2 plasma. After growth, a capping agent can be used. For example, vapor of isopropyltris(dimethylamino)tin may be flowed over the surface.

[0265] The deposition process can be used on any useful surface. As referred to herein, a "surface" is a surface on which the film of the present technology is deposited or is exposed to EUV during processing. Such a surface can be on a substrate (e.g., on which a film is deposited) or on a film (e.g., on which a capping layer can be deposited).

[0266] Any useful substrate can be used, including any material structure suitable for lithographic processing, particularly for the manufacture of integrated circuits and other semiconductor devices. In some embodiments, the substrate is a silicon wafer. The substrate can be a silicon wafer on which features having irregular surface topography ("underlying topographical features") are formed.

[0267] Such underlying topographical features may include areas where material has been removed (e.g., by etching) or where material has been added (e.g., by deposition) during processing prior to performing the method of the present technology. Such pre-processing may include other processing methods of the present technology or in an iterative process, whereby two or more layers of features are formed on the substrate. Without limiting the mechanism, function, or utility of the present technology, in some embodiments, the method of the present technology is believed to provide advantages over methods known in the art that deposit photolithographic films onto the surface of a substrate using spin casting methods. Such advantages may derive from the conformity of the film of the present technology to the underlying features without "filling" or planarizing such features, and the ability to deposit films onto a wide variety of material surfaces.

[0268] In some embodiments, the substrate is a hard mask used in the lithographic etching of the underlying semiconductor material. Hard masks can be made of materials such as amorphous carbon (aC), tin oxide (e.g., SnO x ), silicon oxide (e.g., SiO2), silicon oxynitride (e.g., SiO x N y ), silicon oxycarbide (e.g., SiO x C y ), silicon nitride (e.g., Si3N4), titanium oxide (e.g., TiO2), titanium nitride (e.g., TiN), tungsten (e.g., W), doped carbon (e.g., W-doped C), tungsten oxide (e.g., WO x The substrate may comprise any of a variety of materials, including, for example, SiO 2 , hafnium oxide (e.g., HfO 2 ), zirconium oxide (e.g., ZrO 2 ), and aluminum oxide (e.g., Al 2 O 3 ). For example, the substrate is preferably a SnO 2 , such as SnO 2 . x In various embodiments, the layer can be from 1 nm to 100 nm thick, or from 2 nm to 10 nm thick.

[0269] In some non-limiting embodiments, the substrate includes an underlayer. The underlayer may be deposited on a hard mask or other layer, and generally underlies the resist film (or imaging layer) described herein. The underlayer may be used to improve the sensitivity of the PR, increase the EUV absorption rate, and / or increase the patterning performance of the PR. If there are device features present on the substrate to be patterned that form significant topography, another important function of the underlayer is that it can overcoat and planarize the existing topography, so that subsequent patterning steps can be performed on a flat surface with all areas of the pattern in focus. In such applications, the underlayer (or at least one of the underlayers) may be applied using spin-coating techniques. If the PR material used has a significant inorganic component, e.g., exhibits a predominantly metal oxide framework, the underlayer may advantageously be a carbon-based film applied by either spin-coating or a dry vacuum-based deposition process. The layers can include a variety of ashable hardmask (AHM) films having carbon-based and hydrogen-based compositions, and can be doped with additional elements such as tungsten, boron, nitrogen, or fluorine.

[0270] In various embodiments, the surface (e.g., of a substrate and / or film) includes exposed hydroxyl groups on its surface. In general, the surface can be any surface that includes or has been treated to provide an exposed hydroxyl surface. Such hydroxyl groups can be formed on the surface by surface treatment of the substrate using oxygen plasma, water plasma, or ozone. In other embodiments, the surface of the film can be treated to provide exposed hydroxyl groups, over which a capping layer can be applied. In various embodiments, the hydroxyl-terminated metal oxide layer has a thickness of 0.1 nm to 20 nm, or 0.2 nm to 10 nm, or 0.5 nm to 5 nm.

[0271] EUV exposure process EUV exposure of the membrane can provide EUV-exposed regions with activated reactive centers containing a metal atom (M) resulting from an EUV-mediated cleavage event. Such reactive centers can include a dangling metal bond, a M-H group, a cleaved M-ligand group, a dimerized M-M bond, or a M-O-M bridge.

[0272] The EUV exposure can have a wavelength in the range of about 10 nm to about 20 nm, for example, 10 nm to 15 nm, for example, 13.5 nm, in a vacuum atmosphere. In particular, the patterning can provide EUV exposed areas and EUV non-exposed areas to form a pattern.

[0273] The present techniques can include patterning using EUV, as well as DUV or e-beam. In such patterning, radiation is focused on one or more regions of the resist film. Exposure can be performed such that the resist film includes one or more regions that are not exposed to radiation. The resulting resist film can include multiple exposed and unexposed regions, forming a pattern consistent with the formation of transistors or other features of a semiconductor device that are formed by adding or removing material from the substrate in subsequent processing of the substrate. EUV, DUV, and e-beam radiation methods and equipment useful herein include methods and equipment known in the art.

[0274] In some EUV lithography techniques, an organic hardmask (e.g., a PECVD amorphous hydrogenated carbon ashable hardmask) is patterned using a photoresist process. During photoresist exposure, EUV radiation is absorbed by the resist and the underlying substrate, generating high-energy photoelectrons (e.g., about 100 eV) and then a cascade of lower-energy secondary electrons (e.g., about 10 eV) that diffuse laterally by a few nanometers. These electrons increase the extent of chemical reactions in the resist and increase its EUV dose sensitivity. However, an essentially random secondary electron pattern is superimposed on the optical image. This undesirable secondary electron exposure results in loss of resolution, observable line edge roughness (LER), and linewidth variations in the patterned resist. These defects are replicated in the material being patterned during the subsequent pattern-transfer etch.

[0275] Disclosed herein is a vacuum-integrated metal hardmask process and associated vacuum-integrated hardware that combines film formation (deposition / condensation) and optical lithography, resulting in significantly improved EUV lithography (EUVL) performance, e.g., reduced line edge roughness.

[0276] In various embodiments described herein, a deposition (e.g., condensation) process (e.g., ALD or MOCVD performed in a PECVD tool such as a Lam Vector®) can be used to form a thin film of a metal-containing film, such as a photosensitive metal salt or metal-containing organic compound (organometallic compound), that has strong absorption in the EUV (e.g., at wavelengths on the order of 10 nm to 20 nm), for example at the wavelength of an EUVL light source (e.g., 13.5 nm = 91.8 eV). This film photodecomposes upon EUV exposure and forms a metal mask that is a pattern transfer layer during subsequent etching (e.g., in a conductor etch tool such as a Lam 2300® Kiyo®).

[0277] Following deposition, the EUV-patternable thin film is patterned by exposure to a beam of EUV light, optionally under a relatively high vacuum. For EUV exposure, the metal-containing film may be deposited in a chamber integrated with the lithography platform (e.g., a wafer stepper such as the TWINSCAN NXE:3300B platform supplied by ASML, Veldhoven, The Netherlands) and transferred under vacuum so as not to react prior to exposure. Integration with the lithography tool is facilitated by the fact that EUVL also requires a significantly reduced pressure, given the strong optical absorption of incident photons by ambient gases such as H2O, O2, etc. In other embodiments, photosensitive metal film deposition and EUV exposure can occur in the same chamber.

[0278] Development process, including wet or dry development The EUV exposed or unexposed areas, as well as the absorber layer, can be removed by any useful development process. In one embodiment, the EUV exposed regions can have activated reactive centers, such as dangling metal bonds, M-H groups, or dimerized M-M bonds. Such reactive centers can further react to form densified regions within the EUV exposed regions. In some embodiments, the EUV exposed regions are retained and the EUV unexposed regions are transferred using dry or wet development.

[0279] In certain embodiments, the MH groups can be selectively removed by using one or more dry development processes (e.g., halide chemistries). In other embodiments, the MM bonds can be selectively removed by using a development process to form soluble M(OH) groups, for example, using hot ethanol and water. n It is possible to selectively remove the EUV-exposed regions by providing groups. In yet other embodiments, the EUV-exposed regions are removed by using development (e.g., by using a positive tone developer). In some embodiments, the EUV-unexposed regions are removed by using dry development.

[0280] As described herein, a dry development process can be used to treat the film (e.g., dry development can be used alone, before wet development, after wet development, before wet processing, or before dry processing). Non-limiting dry development processes can include the use of halides, such as HCl-based or HBr-based processes. Although this disclosure is not limited to a particular theory of operation or mechanism, it is understood that the approach leverages the chemical reactivity of the dry-deposited EUV photoresist film with clean chemicals (e.g., HCl, HBr, and BCl3) to form volatile products using steam or plasma. Such volatile products can be removed in any manner (e.g., by treating with an aqueous acid as described herein). Dry-deposited EUV photoresist films can be removed at etch rates of up to 1 nm / sec. Rapid removal of dry-deposited EUV photoresist films with these chemicals is applicable for chamber cleaning, backside cleaning, bevel cleaning, and PR development. The film can be removed using steam at various temperatures (e.g., HCl or HBr at temperatures above -10°C, or BCl3 at temperatures above 80°C), but plasma can also be used to further accelerate or enhance the reactivity.

[0281] Plasma processes include transformer coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP) using equipment and techniques known in the art. For example, the process can be performed at a pressure of >0.5 mTorr (e.g., 1 mTorr to 100 mTorr, etc.) and a power level of <1000 W (e.g., <500 W). The temperature can be 30° C. to 300° C. (e.g., 30° C. to 120° C.) for a time of 1 to 3000 seconds (e.g., 10 seconds to 600 seconds), with a flow rate of 100 to 1000 standard cubic centimeters per minute (sccm), e.g., about 500 sccm.

[0282] When the halide reactant flow is hydrogen gas and halide gas, remote plasma / UV radiation is used to generate radicals from H2 and Cl2 and / or Br2, and the hydrogen and halide radicals are flowed into the reaction chamber and contacted with the patterned EUV photoresist on the substrate layer of the wafer. Suitable plasma powers can range from 100W to 500W, without bias. These conditions are suitable for some processing reactors, e.g., Kiyo etch tools available from Lam Research, Inc., Fremont, Calif., but it should be understood that a wider range of process conditions can be used depending on the capabilities of the processing reactor.

[0283] In a thermal development process, the substrate is exposed to a dry development chemical (e.g., Lewis acid) in a vacuum chamber (e.g., oven). A suitable chamber can include a vacuum line, a dry development hydrogen halide chemical gas (e.g., HBr, HCl) line, and a heater for temperature control. In some embodiments, the chamber interior can be coated with a corrosion resistant film, such as an organic polymer or inorganic coating. One such coating is polytetrafluoroethylene ((PTFE), e.g., Teflon™). Such materials can be used in the thermal processes of the present disclosure without the risk of removal by plasma exposure.

[0284] The process conditions for dry development can be about 10 seconds to 1 minute without plasma, reactant flow rates of 100 sccm to 500 sccm (e.g., 500 sccm HBr or HCl), temperatures of -10°C to 120°C (e.g., -10°C), and pressures of 1 mTorr to 500 mTorr (e.g., 300 mTorr), depending on the photoresist films and their composition and properties.

[0285] In various embodiments, the disclosed method combines all dry steps of film deposition, vapor deposition formation, (EUV) lithography photopatterning, and dry development. In such a process, the substrate can go directly to a dry development / etching chamber following photopatterning in an EUV scanner. Optionally, dry treatment with acid vapor is performed after dry development. In other embodiments, wet treatment with acid solution is performed after dry development.

[0286] In other embodiments, the disclosed method combines all dry steps of film deposition, vapor deposition formation, and (EUV) lithography photopatterning, followed by wet development. Optionally, a dry treatment with acid vapor is performed after wet development. In other embodiments, a wet treatment with an acid solution is performed after wet development.

[0287] In various embodiments, the EUV photoresist containing some amount of metal, metal oxide, and organic components has the formula R x Z y Dry development can be achieved by thermal, plasma (including possible photoactivated plasma, e.g., lamp-heated or UV-lamp-heated), or a combination of thermal and plasma methods, while flowing a dry development gas containing a compound of the formula: R = B, Al, Si, C, S, SO, x > 0, Z = Cl, H, Br, F, CH4, y > 0. Dry development can be achieved by flowing a dry development gas containing a compound of the formula: R x Z y The species can selectively remove the exposed material, resulting in a positive tone, leaving the unexposed counterpart as a mask. In some embodiments, the exposed portions of the organotin oxide-based photoresist film are removed by dry development in accordance with the present disclosure. Positive tone dry development can be achieved by selective dry development (removal) of the EUV-exposed areas that are exposed to a flow of hydrogen halides or hydrogen and halides (including HCl and / or HBr) without applying a plasma, or a flow of H2 and Cl2 and / or Br2 using UV radiation generated from a remote plasma or plasma to generate radicals.

[0288] Wet development methods can also be used, in certain embodiments, to remove the EUV exposed areas to provide a negative or positive resist. Exemplary non-limiting wet development may include the use of developers (e.g., aqueous acidic developers, non-aqueous acidic developers, or acidic developers in organic solvents) that include halides (e.g., HF, HCl, or HBr), organic acids (e.g., formic acid, acetic acid, oxalic acid, or citric acid), or organic halide compounds (e.g., organic fluorine compounds, organic chlorine compounds, organic bromine compounds, or organic iodine compounds, including trifluoroacetic acid), or the use of organic developers, such as alcohols (e.g., isopropyl alcohol (IPA)), ketones (e.g., 2-heptanone, cyclohexanone, or acetone), ethers, such as glycol ethers (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA)), or esters (e.g., γ-butyrolactone or 3-ethyl ethoxypropionate (EEP)), as well as combinations thereof. Other acids (e.g., aqueous acid solutions) are described herein. Non-limiting combinations include water and an acid developer.

[0289] In some embodiments, wet development includes a neutral developer (eg, a pH neutral developer such as water) or a peroxide-containing developer (eg, containing hydrogen peroxide, H2O2).

[0290] Other development methodologies include aqueous developers, non-aqueous developers, alkaline developers (e.g., aqueous alkaline developers or non-aqueous alkaline developers), such as ammonium, e.g., ammonium hydroxide ([NH4] + [OH] -), ammonium-based ionic liquids such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), or other quaternary alkylammonium hydroxides, organic amines such as mono-, di-, and tri-organic amines (e.g., dimethylamine, diethylamine, ethylenediamine, triethylenetetramine), or alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, or diethyleneglycolamine. In other embodiments, the alkaline developer may include the use of a developer comprising a nitrogen-containing base, such as an amine of the formula R N1 NH2, R N1 R N2 N.H., R. N1 R N2 R N3 N, or R N1 R N2 R N3 R N4 N + X N1- and R N1 , R N2 , R N3 , and R N4 Each of X is independently an organic substituent (e.g., an optionally substituted alkyl, an optionally substituted hydroxyalkyl, or any of those described herein), or two or more organic substituents which can be linked together; N1- OH - , F - , Cl - , Br - , I - or other quaternary ammonium cation species known in the art. These bases may also include heterocyclyl nitrogen compounds known in the art, some of which are described herein. Non-limiting combinations include water and a basic developer.

[0291] Yet other development methodologies may include the use of deprotection solvents. Non-limiting deprotection solvents include organic acids (e.g., any of those described herein, such as oxalic acid), or choline hydroxide ([N(CH3)3CH2CH2OH] + [OH] - ) and choline ([N(CH3)3CH2CH2OH] + ) are mentioned.

[0292] The developer can be used in any useful concentration. In one embodiment, the developer comprises from about 0.5% to about 30% by weight of the developer in a solvent (e.g., an aqueous solvent, a non-aqueous solvent, an organic solvent, or a combination thereof), including concentrations from about 1% to about 20% by weight and 1.1% to 10% by weight.

[0293] The developer may be used with one or more additives, such as oxidizing agents, surfactants, salts, and chelating agents. The additives may optionally be present in the developer solution in an amount of less than 10% by weight or less than 5% by weight. Non-limiting oxidizing agents include peroxides or peracids, such as hydrogen peroxide, benzoyl peroxide, urea peroxide, or mixtures thereof.

[0294] Any of the developers herein may include one or more surfactants. The surfactants may include a positive, negative, or neutral charge and may be selected from the group consisting of fluorinated or non-fluorinated surfactants. Non-limiting surfactants include anionic, cationic, and nonionic surfactants, such as alkylphenol ethoxylates (e.g., Triton™ X-100 (polyethylene glycol tert-octylphenyl ether), octylphenol ethoxylate, or nonylphenol ethoxylate), alcohol ethoxylates (e.g., BRIJ® 56 (C 16 H 33 (OCH2CH2) 10 OH), BRIJ® 58 (C 16 H 33 (OCH2CH2) 20OH), or fatty alcohol ethoxylates), fatty acid ethoxylates, poloxamers, fatty acid esters of glycerol, acetylenic diols, amine ethoxylates, glucosides, glucamides, polyethylene glycols, or poly(ethylene glycol-co-propylene glycol), perfluoroalkyl ammonium (e.g., perfluoroalkyl ammonium sulfonates or carboxylates), and combinations thereof.

[0295] Non-limiting salts include cations selected from the group of ammonium, d-block metal cations (such as hafnium, zirconium, lanthanum, etc.), f-block metal cations (such as cerium, lutetium, etc.), p-block metal cations (such as aluminum, tin, etc.), alkali metals (such as lithium, sodium, potassium, etc.), and combinations thereof, and anions selected from the group of fluoride, chloride, bromide, iodide, nitrate, sulfate, phosphate, silicate, borate, peroxide, butoxide, formate, oxalate, ethylenediaminetetraacetic acid (EDTA), tungstate, molybdate, etc., and combinations thereof. Non-limiting chelating agents can include polyamines, alcohol amines, amino acids, carboxylic acids, or combinations thereof.

[0296] In certain embodiments, the positive developer is an acid developer in an aqueous solvent, an acid developer in an organic solvent, an aqueous alkaline developer (e.g., containing NH4OH, TMAH, TEAH, TPAH, or TBAH, with or without H2O2), an aqueous acid developer (e.g., containing HCl or HF), an organic developer, or a deprotection solvent (e.g., containing oxalic acid, choline, or choline hydroxide). The developer can include one solvent or a combination of solvents.

[0297] Wet development can include any useful process, including immersion development, puddle development, and spray development. After or during any of these processes, the substrate can be spun to remove the dissolved portions of the film while simultaneously drying the film.

[0298] The development process can include both wet and dry development processes. Such a process can include an initial wet development followed by a later dry development, or vice versa. Development can also be performed in cycles where multiple wet development processes are used, or multiple dry development processes are used, or multiple wet and dry development processes are employed.

[0299] Other processes The method may include any other useful processes, as described below.

[0300] In the backside and bevel cleaning process, the vapor and / or plasma can be confined to specific areas of the wafer to ensure that only the backside and bevel are removed without degrading the film on the front side of the wafer. The EUV photoresist film being removed is generally composed of Sn, O, and C, but the same cleaning approach can be extended to films of other metal oxide resists and materials. In addition, this approach can also be used for film strip and PR rework.

[0301] Suitable process conditions for dry bevel edge and backside cleaning may be reactant flow rates of 100 sccm to 500 sccm (e.g., 500 sccm HCl, HBr, or H2 and Cl2 or Br2, BCl3 or H2) for a time of about 10 seconds to 20 seconds, depending on the photoresist film and composition and properties, temperatures of -10°C to 120°C (e.g., 20°C), pressures of 20 mTorr to 500 mTorr (e.g., 300 mTorr), plasma powers of 0 to 500 W at high frequency (e.g., 13.56 MHz). These conditions are suitable for some processing reactors, e.g., Kiyo etch tools available from Lam Research, Inc., Fremont, Calif., but it should be understood that a wider range of process conditions may be used depending on the capabilities of the processing reactor.

[0302] Photolithography processes may involve one or more bake steps to promote the chemical reactions necessary to produce chemical contrast between exposed and unexposed areas of the photoresist. For high volume manufacturing (HVM), such bake steps may be performed on a track where the wafer is baked on a hotplate at a preset temperature under ambient air or possibly N2 flow. More careful control of the bake atmosphere during these bake steps, as well as the introduction of additional reactive gas components into the atmosphere, may help to further reduce dose requirements and / or improve pattern fidelity.

[0303] According to various aspects of the present disclosure, one or more post-treatments on metal and / or metal oxide based photoresists after deposition (e.g., post-apply bake (PAB) or another post-apply treatment) and / or exposure (e.g., post-exposure bake (PEB), which can be omitted, or another post-exposure treatment) and / or development (e.g., post-develop bake (PDB) or another post-development treatment) can increase the difference in material properties between exposed and unexposed photoresists, thus reducing dose-to-size (DtS), improving PR profile, and improving line edge and width roughness (LER / LWR) after subsequent dry development. Such treatments can involve thermal processes that control temperature, gas atmosphere, and moisture, resulting in improved dry development performance in subsequent processing. In some cases, remote plasma may be used. In more specific cases, PAB and / or PEB and / or PDB are not performed.

[0304] For post-application treatments (e.g., PAB), thermal processes that control temperature (e.g., with heating or cooling), gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, NO, NO, Ar, He, or mixtures thereof) or under vacuum, and moisture can be used after deposition and before exposure to change the composition of the unexposed metal and / or metal oxide photoresist. This change can increase the EUV sensitivity of the material, and thus achieve reduced dose-to-size and edge roughness after exposure and dry development.

[0305] For post-exposure treatment (e.g., PEB), a thermal process that controls temperature, gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, NO, Ar, He, or mixtures thereof) or under vacuum, and moisture can be used to change the composition of both the unexposed and exposed photoresist. This change can increase the difference in composition / material properties between the unexposed and exposed photoresist, and the difference in the etch rate of the dry development etch gas between the unexposed and exposed photoresist. Thereby, higher etch selectivity can be achieved. The improved selectivity can result in a more square PR profile with improved surface roughness and / or less photoresist residue / scum. In certain embodiments, the PEB can be performed in air and in the optional presence of moisture and CO2. In other embodiments, the PEB can be omitted.

[0306] For post-development treatments (e.g., post-develop bake or PDB), the composition of the unexposed photoresist can be altered using a thermal process that controls temperature, gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, NO, Ar, He, or mixtures thereof) or under vacuum (e.g., using UV), and moisture. In certain embodiments, the conditions also include the use of plasma (e.g., including O2, O3, Ar, He, or mixtures thereof). This change can increase the hardness of the material, which can be beneficial if the film is used as a resist mask in etching the underlying substrate.

[0307] In these cases, in alternative embodiments, the thermal process can be replaced with a remote plasma process to increase the reactive species, lowering the energy barrier to the reaction and increasing productivity. Remote plasma can generate more reactive radicals, thus lowering the reaction temperature / time for the process, leading to increased productivity.

[0308] Thus, one or more processes can be applied to modify the photoresist itself to increase the selectivity of dry or wet development. This thermal or radical modification can increase the contrast between the unexposed and exposed materials, and thus the selectivity of the subsequent development step. The resulting difference between the material properties of the unexposed and exposed materials can be adjusted by adjusting process conditions including temperature, gas flow, moisture, pressure, and / or RF power.

[0309] For dry or wet developed resist films, the treatment temperature in PAB, PEB, or PDB can be varied, for example, from about 90° C. to 250° C. for PAB, and from about 170° C. to 250° C. or higher for PEB and / or PDB, to adjust and optimize the treatment process. In certain embodiments, the PEB is omitted.

[0310] In certain embodiments, the PAB, PEB, and / or PDB treatments can be performed at a gas atmosphere flow ranging from 100 sccm to 10,000 sccm, with a water content in the amount of a few percent up to 100% (e.g., 20% to 50%), at a pressure between atmospheric pressure and vacuum, for a period of about 30 seconds to 15 minutes, e.g., about 1 to 2 minutes. In certain embodiments, the PEB is omitted.

[0311] These findings can be used to adjust process conditions to tailor or optimize processes for specific materials and circumstances. For example, the selectivity achieved for a given EUV dose with a PEB thermal treatment of 220°C-250°C in air at about 20% humidity for about 2 minutes can be similar to that for about 30% higher EUV doses without such thermal treatment. Depending on the selectivity requirements / constraints of the semiconductor processing operation, thermal treatments as described herein can be used to lower the required EUV dose. Alternatively, if higher selectivity is required and a higher dose can be tolerated, much higher selectivity (up to 100x exposed vs. unexposed) can be obtained.

[0312] Yet other steps may include in situ metrology capable of assessing physical and structural properties (e.g., critical dimensions, film thickness, etc.) during the photolithography process. Modules for performing in situ metrology may include, for example, a scatterometry module, an ellipsometry module, a downstream mass spectrometry module, and / or a plasma-enhanced downstream optical emission spectroscopy module.

[0313] 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 with a chamber for depositing one or more precursors to provide a film, a patterning module with an EUV photolithography tool with a radiation source with a wavelength of less than 30 nm, and a development module with a chamber for developing the film (e.g., with an acid or any of the development chemistries described herein). Post-development treatment (e.g., with an acid) can be performed in the development module, in a separate process chamber, or in a separate processing module.

[0314] The apparatus may further include a controller having instructions for such modules. In one embodiment, the controller includes one or more memory devices, one or more processors, and system control software coded with instructions for depositing the film. Such instructions may include depositing one or more precursors to provide a film and optionally PAB or post-application treatment of the film in a deposition module, patterning the film with a resolution of less than 30 nm directly by EUV exposure to thereby form a pattern in the film in a patterning module, and developing the film in a development module. In a particular embodiment, the development module provides removal of EUV exposed or non-EUV exposed areas, thereby providing a pattern in the film. The development module may include developing the pattern in the presence of an acid.

[0315] In another embodiment, the apparatus further includes a post-development treatment module that can provide a process chamber for post-development treatment of the film. Any post-development process herein can be performed in the post-development treatment module, which can include performing an acid treatment of the pattern, a post-development bake (PDB) operation, a plasma-based etch process, and / or other operations described herein.

[0316] FIG. 6 illustrates a schematic diagram of one embodiment of a process station 600 having a process chamber body 602 for maintaining a low pressure environment suitable for carrying out the dry deposition and development embodiments described herein. Multiple process stations 600 may be included in a common low pressure process tool environment. For example, FIG. 7 illustrates one embodiment of a multi-station processing tool 700, such as a VECTOR® processing tool available from Lam Research, Inc. of Fremont, Calif. In some embodiments, one or more hardware parameters of the process station 600 (including those described in detail below) may be programmatically adjusted by one or more computer controllers 650.

[0317] The process stations can be configured as modules within a cluster tool. Figure 9 illustrates a semiconductor process cluster tool architecture having a vacuum integrated deposition and patterning module suitable for carrying out the embodiments described herein. Such a cluster process tool architecture can include a resist deposition module, a resist exposure (EUV scanner) module, a resist development module, and / or an etch module, as described above and further below with reference to Figures 6, 8, and 10.

[0318] In some embodiments, certain processing functions, such as dry developing and etching, can be performed sequentially in the same module. Also, embodiments of the present disclosure are directed to methods and apparatus for receiving a wafer including a photo-patterned EUV resist thin film layer disposed on a layer or layer stack to be etched, following photo-patterning in an EUV scanner, into a dry developing / etching chamber, dry developing the photo-patterned EUV resist thin film layer, and then etching the underlying layer using the patterned EUV resist as a mask, as described herein.

[0319] In other embodiments, an all-dry process is used. An embodiment of the present disclosure may be directed to a method and apparatus for receiving a wafer including a photo-patterned EUV resist thin film layer disposed on a layer or layer stack to be etched into a dry development / etch chamber following photo-patterning in an EUV scanner, dry developing the photo-patterned EUV resist thin film layer, and then treating the patterned EUV resist in a dry treatment process including acid. In certain cases, the dry development includes acid, and the dry treatment process may be optionally omitted. In other examples, the dry development may or may not include acid, and the dry treatment is performed in the presence of acid.

[0320] In other embodiments, different modules may be used, especially when a dry process is followed by a wet process or vice versa. Non-limiting embodiments of the present disclosure are directed to methods and apparatus for receiving a wafer, depositing an EUV resist thin film layer in a dry deposition process (e.g., using vapor) or a wet deposition process (e.g., using liquid), followed by photopatterning in an EUV scanner, and then wet or dry developing the photopatterned EUV resist thin film layer (e.g., optionally with acid), as described herein. Other non-limiting embodiments of the present disclosure are directed to methods and apparatus for receiving a wafer, depositing an EUV resist thin film layer in a dry deposition process or a wet deposition process, followed by photopatterning in an EUV scanner, developing the photopatterned EUV resist thin film layer, and then processing the pattern in a dry or wet processing process including acid, as described herein.

[0321] Returning to FIG. 6, the process station 600 is in fluid communication with a reactant delivery system 601a for delivering process gases to a distribution showerhead 606. The reactant delivery system 601a optionally includes a mixing vessel 604 for blending and / or adjusting the process gases delivered to the showerhead 606. One or more mixing vessel inlet valves 620 can control the introduction of process gases to the mixing vessel 604. If plasma exposure is used, the plasma can also be delivered to the showerhead 606 or can be generated at the process station 600. As noted above, in at least some embodiments, non-plasma thermal exposure is preferred.

[0322] 6 includes an optional vaporization point 603 for vaporizing the liquid reactant provided to the mixing vessel 604. In some embodiments, a liquid flow controller (LFC) can be provided upstream of the vaporization point 603 to control the mass flow rate of the liquid that is vaporized and delivered to the process station 600. For example, the LFC can include a thermal mass flow meter (MFM) located downstream of the LFC. A plunger valve of the LFC can then be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM.

[0323] The showerhead 606 distributes process gases towards the substrate 612. In the embodiment illustrated in Figure 6, the substrate 612 is shown positioned below the showerhead 606 and resting on a pedestal 608. The showerhead 606 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to the substrate 612.

[0324] In some embodiments, the pedestal 608 can be raised or lowered to expose the substrate 612 to the volume between the substrate 612 and the showerhead 606. It will be appreciated that in some embodiments, the height of the pedestal can be programmatically adjusted by a suitable computer controller 650.

[0325] In some embodiments, the pedestal 608 may be temperature controlled via heater 610. In some embodiments, the pedestal 608 may be heated to a temperature of greater than 0° C. to 300° C. or greater, such as 50-120° C., such as about 65-80° C., during non-plasma thermal exposure of the photopatterned resist to a hydrogen halide dry developing chemistry, such as HBr, HCl, or BCl3, as described in disclosed embodiments.

[0326] Additionally, in some embodiments, pressure control for the process station 600 may be provided by a butterfly valve 618. As shown in the embodiment of Figure 6, the butterfly valve 618 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control for the process station 600 may also be adjusted by varying the flow rate of one or more gases introduced to the process station 600.

[0327] In some embodiments, the position of the showerhead 606 can be adjusted relative to the pedestal 608 to vary the volume between the substrate 612 and the showerhead 606. Further, it will be appreciated that the vertical position of the pedestal 608 and / or the showerhead 606 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 608 may include a rotational axis for rotating the orientation of the substrate 612. It will be appreciated that in some embodiments, one or more of these exemplary adjustments can be implemented programmatically by one or more suitable computer controllers 650.

[0328] When plasma may be used, for example in a gentle plasma-based dry development embodiment and / or an etching operation performed in the same chamber, the showerhead 606 and pedestal 608 are in electrical communication with a radio frequency (RF) power source 614 and matching network 616 to power the plasma. In some embodiments, the plasma energy can be controlled by controlling one or more of the process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power source 614 and matching network 616 can be operated at any suitable power to form a plasma having a desired composition of radical species. An example of a suitable power is up to about 500 W.

[0329] In some embodiments, instructions for the controller 650 may be provided via input / output control (IOC) sequence instructions. In one example, instructions for setting conditions for a process step may be included in a corresponding recipe step of a process recipe. In some cases, a process recipe step may be arranged in sequence such that all instructions for a process step are executed simultaneously with that process step. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe step. For example, a recipe step may include instructions for setting a flow rate of a dry development chemical reactant gas, such as HBr or HCl, and a time delay instruction for the recipe step. In some embodiments, the controller 650 may include any of the features described below with respect to the system controller 750 of FIG. 7.

[0330] As mentioned above, one or more process stations can be included in a multi-station processing tool. FIG. 7 shows a schematic diagram of an embodiment of a multi-station processing tool 700 with an inbound load lock 702 and an outbound load lock 704, either or both of which may include a remote plasma source. A robot 706 is configured to move a wafer from a cassette loaded via a pod 708 at atmospheric pressure to the inbound load lock 702 via an atmospheric pressure port 710. The wafer is placed by the robot 706 on a pedestal 712 of the inbound load lock 702, the atmospheric pressure port 710 is closed, and the load lock is pumped down. If the inbound load lock 702 includes a remote plasma source, the wafer may be subjected to a remote plasma treatment to treat the silicon nitride surface within the load lock before being introduced to the processing chamber 714. Additionally, the wafer may also be heated in the inbound load lock 702 to remove, for example, moisture and absorbed gases. A chamber transfer port 716 to the processing chamber 714 is then opened and another robot (not shown) places the wafer into the reactor on the pedestal of the first station shown in the reactor for processing. Although the embodiment shown in Figure 7 includes a load lock, it will be understood that in some embodiments the wafer may enter the process station directly.

[0331] The illustrated processing chamber 714 includes four process stations, numbered 1 through 4 in the embodiment shown in FIG. 7. Each station has a heated pedestal (shown at 718 for station 1) and a gas line inlet. It will be appreciated that in some embodiments, each process station may have a different purpose or multiple purposes. For example, in some embodiments, a process station may be switchable between a dry development mode and an etch process mode. Additionally or alternatively, in some embodiments, the processing chamber 714 may include one or more corresponding pairs of dry development and etch process stations. While the illustrated processing chamber 714 includes four stations, it will be appreciated that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments, a processing chamber may have three or fewer stations.

[0332] FIG. 7 illustrates one embodiment of a wafer handling system 790 for transferring wafers within the processing chamber 714. In some embodiments, the wafer handling system 790 can transfer wafers between various process stations and / or between process stations and load locks. It will be understood that any suitable wafer handling system may be used. Non-limiting examples include a wafer carousel and a wafer handling robot. FIG. 7 also illustrates one embodiment of a system controller 750 used to control the process conditions and hardware states of the process tool 700. The system controller 750 can include one or more memory devices 756, one or more mass storage devices 754, and one or more processors 752. The processor 752 can include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0333] In some embodiments, the system controller 750 controls all of the activity of the process tool 700. The system controller 750 executes system control software 758 that is stored in the mass storage device 754, loaded into the memory device 756, and executed on the processor 752. Alternatively, the control logic may be hard-coded into the controller 750. Application specific integrated circuits, programmable logic devices (e.g., field programmable gate arrays, or FPGAs), and the like may be used for these purposes. In the following description, wherever "software" or "code" is used, functionally equivalent hard-coded logic may be used instead. The system control software 758 may include instructions for controlling the timing, mixture of gases, gas flow rates, chamber and / or station pressures, chamber and / or station temperatures, wafer temperatures, target power levels, RF power levels, substrate pedestal, chuck and / or susceptor positions, and other parameters of a particular process performed by the process tool 700. The system control software 758 may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be written to control the operation of the process tool components used to perform the various process tool processes. The system control software 758 may be coded in any suitable computer readable programming language.

[0334] In some embodiments, the system control software 758 may include input / output control (IOC) sequence instructions for controlling the various parameters described above. In some embodiments, other computer software and / or programs stored on the mass storage device 754 and / or memory device 756 associated with the system controller 750 may be used. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0335] The substrate positioning program may include program code for process tool components used to load the substrate onto the pedestal 718 and control the spacing between the substrate and other parts of the process tool 700.

[0336] The process gas control program may include code for controlling hydrogen halide gas composition (e.g., HBr or HCl gas as described herein) and flow rates to stabilize the pressure of the process station, and optionally, code for flowing gas to one or more process stations prior to deposition. The pressure control program may include code for controlling the pressure of the process station, for example, by adjusting a throttle valve in the exhaust system of the process station, gas flow to the process station, etc.

[0337] The heater control program may include code for controlling the current to a heating unit used to heat the substrate, or the heater control program may control the delivery of a heat transfer gas (such as helium) to the substrate.

[0338] The plasma control program can include code for setting RF power levels applied to process electrodes in one or more process stations in accordance with embodiments herein.

[0339] The pressure control program can include code for maintaining pressure in the reaction chamber according to embodiments herein.

[0340] In some embodiments, there may be a user interface associated with the system controller 750. The user interface may include a display screen, a graphical software display of equipment and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0341] In some embodiments, the parameters adjusted by the system controller 750 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF bias power levels), etc. These parameters may be provided to a user in the form of a recipe and may be entered using a user interface.

[0342] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 750 from various process tool sensors. Signals for controlling the process can be output at analog and digital output connections of the process tool 700. Non-limiting examples of process tool sensors that can be monitored include mass flow controllers, pressure sensors (such as pressure gauges), thermocouples, etc. Appropriately programmed feedback and control algorithms can be used with data from these sensors to maintain process conditions.

[0343] The system controller 750 can provide program instructions for carrying out the deposition process described above. The program instructions can control various process parameters such as DC power levels, RF bias power levels, pressure, temperature, etc. The instructions can control parameters for operating dry development and / or etching processes according to various embodiments described herein.

[0344] The system controller 750 includes one or more memory devices and one or more processors configured to execute instructions such that the apparatus performs methods according to the disclosed embodiments. A machine-readable medium including instructions for controlling process operations according to the disclosed embodiments may be coupled to the system controller 750.

[0345] In some implementations, the system controller 750 is part of a system, such a system may be part of the examples described above. Such a system may include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more processing platforms, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling system operations before, during, and after processing of a semiconductor wafer or substrate. Such electronics may be referred to as a "controller" and may control various components or subparts of one or more systems. The system controller 750 may be programmed to control any of the processes disclosed herein depending on the processing conditions and / or type of system. Such processes may include delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and motion settings, wafer loading and unloading to and from tools and other transfer tools connected or interlocked with the particular system, and / or wafer loading and unloading to and from load locks.

[0346] Broadly, the system controller 750 may be defined as electronic equipment having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors, i.e., microcontrollers that execute program instructions (e.g., software). The program instructions may be instructions communicated to the system controller 750 in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for a system. The operational parameters may, in some embodiments, be part of a recipe defined by a process engineer to accomplish one or more processing steps in the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0347] The system controller 750 may in some embodiments be part of, coupled to, or a combination of a computer that is integrated or coupled with the system or otherwise networked to the system. For example, the system controller 750 may be in the "cloud" or may be all or part of a fab host computer system. This allows for remote access of wafer processing. The computer may allow remote access to the system to monitor the current progress of a fabrication operation, review the history of past fabrication operations, review trends or performance criteria from multiple fabrication operations, modify parameters of a current process, set processing steps following a current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide a process recipe to the system over a network. Such a network may include a local network or the Internet. The remote computer may include a user interface that allows entry or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some examples, the system controller 750 receives instructions in the form of data. Such data identifies parameters for each processing step performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool that the system controller 750 is configured to interface with or control. Thus, as described above, the system controller 750 may be distributed, for example, by including one or more individual controllers that are networked together and cooperate toward a common purpose (such as the processes and controls described herein).An example of a distributed controller for such purposes would include one or more integrated circuits on the chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) and coupled to control the process in the chamber.

[0348] Exemplary systems may include, but are not limited to, a plasma etch chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a tracking chamber or module, an EUV lithography chamber (scanner) or module, a dry development chamber or module, and any other semiconductor processing system that may be associated with or used in the fabrication and / or manufacturing of semiconductor wafers.

[0349] As described above, depending on the process step or steps being performed by the tool, system controller 750 may communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, another controller, or tools used for material transport to and from tool locations and / or load ports within a semiconductor manufacturing factory.

[0350] In a particular embodiment, an inductively coupled plasma (ICP) reactor is described herein that may be suitable for etching operations suitable for practicing some embodiments. Although an ICP reactor is described herein, it should be understood that in some embodiments, a capacitively coupled plasma reactor may also be used.

[0351] 8 illustrates generally a cross-sectional view of an inductively coupled plasma apparatus 800 suitable for performing certain embodiments or aspects of embodiments, such as dry development and / or etching, an example of which is the Kiyo® reactor manufactured by Lam Research, Inc. of Fremont, Calif. In other embodiments, other tools or tool types having the functionality to perform the dry development and / or etching processes described herein may be used.

[0352] The inductively coupled plasma apparatus 800 includes an overall process chamber 824 structurally defined by a chamber wall 801 and a window 811. The chamber wall 801 can be fabricated from stainless steel or aluminum. The window 811 can be fabricated from quartz or other dielectric materials. An optional internal plasma grid 850 divides the overall process chamber into an upper subchamber 802 and a lower subchamber 803. In many embodiments, the plasma grid 850 can be removed, thereby utilizing the chamber space consisting of the subchambers 802 and 803. A chuck 817 is positioned within the lower subchamber 803 near the bottom inner surface. The chuck 817 is configured to receive and hold a semiconductor wafer 819 on which the etching and deposition processes are performed. The chuck 817, if present, can be an electrostatic chuck for supporting the wafer 819. In some embodiments, an edge ring (not shown) surrounds the chuck 817 and, if present on the chuck 817, has an upper surface that is approximately planar with an upper surface of the wafer 819. The chuck 817 also includes an electrostatic electrode for chucking and dechucking the wafer 819. For this purpose, a filter and DC clamp power supply (not shown) may be provided. Other control systems for lifting the wafer 819 from the chuck 817 may also be provided. The chuck 817 may be charged using an RF power supply 823. The RF power supply 823 is connected to a matching circuit 821 through a connection 827. The matching circuit 821 is connected to the chuck 817 through a connection 825. In this manner, the RF power supply 823 is connected to the chuck 817. In various embodiments, the bias power of the electrostatic chuck may be set to about 50V or may be set to a different bias power depending on the process to be performed according to the disclosed embodiments. For example, the bias power may be about 20V to about 100V, or about 30V to about 150V.

[0353] The elements for plasma generation include a coil 833 positioned over the window 811. In some embodiments, a coil is not used in the disclosed embodiments. The coil 833 is fabricated from a conductive material and includes at least one complete turn. The exemplary coil 833 shown in FIG. 8 includes three turns. A cross section of the coil 833 is shown symbolically, with the coil having an "X" rotating into the page and the coil having a "●" rotating out of the page. The elements for plasma generation also include an RF power source 841 configured to provide RF power to the coil 833. Generally, the RF power source 841 is connected to a matching circuit 839 through connection 845. The matching circuit 839 is connected to the coil 833 through connection 843. In this manner, the RF power source 841 is connected to the coil 833. An optional Faraday shield 849a is positioned between the coil 833 and the window 811. The Faraday shield 849a may be maintained in a spaced apart relationship relative to the coil 833. In some embodiments, the Faraday shield 849a is disposed directly above the window 811. In some embodiments, the Faraday shield 849b is between the window 811 and the chuck 817. In some embodiments, the Faraday shield 849b is not maintained in a spaced apart relationship to the coil 833. For example, the Faraday shield 849b may be directly below the window 811 without a gap. The coil 833, the Faraday shield 849a, and the window 811 are each configured to be substantially parallel to one another. The Faraday shield 849a may prevent metals or other species from depositing on the window 811 of the process chamber 824.

[0354] Process gases can flow into the process chamber via one or more main gas inlets 860 and / or one or more side gas inlets 870 positioned in the upper subchamber 802. Similarly, similar gas inlets, not explicitly shown, can be used to supply process gases to the capacitively coupled plasma processing chamber. A vacuum pump, e.g., a one or two stage mechanical dry pump and / or turbomolecular pump 840, can be used to draw process gases from the process chamber 824 and maintain pressure within the process chamber 824. For example, the vacuum pump can be used to evacuate the lower subchamber 803 during an ALD purge operation. A valve controlled conduit can be used to fluidly connect the vacuum pump to the process chamber 824 to selectively control application of the vacuum environment provided by the vacuum pump. This can be done with a closed loop controlled flow restriction device, such as a throttle valve (not shown) or a pendulum valve (not shown), during plasma processing operations. Similarly, a vacuum pump and a valve controlled fluid connection to the capacitively coupled plasma processing chamber can also be used.

[0355] During operation of the apparatus 800, one or more process gases may be supplied through the gas inlets 860 and / or 870. In certain embodiments, the process gases may be supplied only through the main gas inlet 860 or only through the side gas inlet 870. In some cases, the gas inlets shown in the figure may be replaced with more complex gas inlets, such as one or more showerheads. The Faraday shield 849a and / or the optional grid 850 may include internal channels and holes that allow delivery of process gases to the process chamber 824. Either or both of the Faraday shield 849a and the optional grid 850 may act as a showerhead for delivering process gases. In some embodiments, a liquid vaporization and delivery system may be located upstream of the process chamber 824, whereby once the liquid reactants or precursors are vaporized, the vaporized reactants or precursors are introduced into the process chamber 824 via the gas inlets 860 and / or 870.

[0356] Radio frequency power is supplied from an RF power supply 841 to the coil 833, causing an RF current to flow through the coil 833. The RF current flowing through the coil 833 generates an electromagnetic field around the coil 833. The electromagnetic field generates an induced current in the upper subchamber 802. Physical and chemical interactions of the various generated ions and radicals with the wafer 819 etch features in the wafer 819 and selectively deposit layers on the wafer 819.

[0357] When a plasma grid 850 is used such that both an upper subchamber 802 and a lower subchamber 803 are present, induced currents act on the gas present in the upper subchamber 802, generating an electron-ion plasma in the upper subchamber 802. The optional internal plasma grid 850 limits the number of thermal electrons in the lower subchamber 803. In some embodiments, the apparatus 800 is designed and operated such that the plasma present in the lower subchamber 803 is an ion-ion plasma.

[0358] Both the upper electron-ion plasma and the lower ion-ion plasma can contain positive and negative ions, but the ion-ion plasma has a greater ratio of negative ions to positive ions. Volatile etch and / or deposition byproducts can be removed from the lower subchamber 803 through port 822. The chuck 817 disclosed herein can operate at elevated temperatures ranging from about 10° C. to about 250° C. The temperature depends on the process operation and the particular recipe.

[0359] The apparatus 800 may be coupled to equipment (not shown) when installed in a clean room or fabrication facility. The equipment includes plumbing to provide process gases, vacuum, temperature control, and environmental particle control. These equipment are coupled to the apparatus 800 when installed in the intended fabrication facility. Additionally, the apparatus 800 may be coupled to a transfer chamber that allows a robot to move semiconductor wafers in and out of the apparatus 800 using automated handling.

[0360] In some embodiments, a system controller 830 (which may include one or more physical or logical controllers) controls some or all of the operation of the process chamber 824. The system controller 830 may include one or more memory devices and one or more processors. In some embodiments, the apparatus 800 includes a switching system for controlling the flow rates and duration when the disclosed embodiments are performed. In some embodiments, the apparatus 800 may have a switching time of up to about 500 ms, or up to about 750 ms. The switching time may depend on the flowing chemistry, the selected recipe, the reactor architecture, and other factors.

[0361] In some implementations, the system controller 830 is part of a system, such a system may be part of the examples described above. Such a system may include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more processing platforms, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling system operations before, during, and after processing of a semiconductor wafer or substrate. Such electronics may be integrated into the system controller 830 and control various components or subparts of one or more systems. The system controller may be programmed to control any of the processes disclosed herein depending on the processing parameters and / or type of system. Such processes may include delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and motion settings, wafer loading and unloading to and from tools and other transfer tools connected or interlocked with the particular system, and / or wafer loading and unloading to and from load locks.

[0362] Broadly, the system controller 830 may be defined as electronic equipment having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors, i.e., microcontrollers that execute program instructions (e.g., software). The program instructions may be instructions communicated to the controller in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for a system. The operational parameters may, in some embodiments, be part of a recipe defined by a process engineer to accomplish one or more processing steps in the fabrication or removal of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0363] The system controller 830 may, in some embodiments, be part of, or coupled to, a computer that is integrated or coupled with the system or otherwise networked to the system, or a combination thereof. For example, the controller may be in the "cloud" or all or part of a fab host computer system. This allows for remote access of wafer processing. The computer may allow remote access to the system to monitor the current progress of a fabrication operation, review the history of past fabrication operations, review trends or performance criteria from multiple fabrication operations, modify parameters of a current process, set processing steps following a current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system over a network. Such a network may include a local network or the Internet. The remote computer may include a user interface that allows entry or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some examples, the system controller 830 receives instructions in the form of data. Such data identifies parameters for each processing step performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool that the controller is configured to interface with or control. Thus, as described above, system controller 830 may be distributed, for example, by including one or more individual controllers that are networked together and cooperate toward a common purpose (such as the processes and controls described herein).An example of a distributed controller for such purposes would include one or more integrated circuits on the chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) and coupled to control the process in the chamber.

[0364] Exemplary systems may include, but are not limited to, a plasma etch chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an ALE chamber or module, an ion implantation chamber or module, a tracking chamber or module, an EUV lithography chamber (scanner) or module, a dry development chamber or module, and any other semiconductor processing system that may be associated with or used in the fabrication and / or manufacturing of semiconductor wafers.

[0365] As described above, depending on the process step or steps being performed by the tool, the controller may communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, another controller, or tools used for material transport to and from tool locations and / or load ports within a semiconductor manufacturing factory.

[0366] EUVL patterning can be performed using any suitable tool, often referred to as a scanner, such as the TWINSCAN NXE:3300B® platform supplied by ASML, Veldhoven, The Netherlands). Processing for deposition, PAB, EUV exposure, development, or other post-development processes (e.g., PDB, plasma etch, acid treatment, etc.) may be performed in separate process chambers and / or the process chambers may be configured as modules in a cluster tool architecture with vacuum integrated deposition and patterning modules suitable for carrying out the embodiments described herein. In some embodiments, certain processing functions, such as dry deposition and PAB, may be performed sequentially in the same chamber or module.

[0367] The EUVL patterning tool may be a stand-alone device from which substrates are loaded and unloaded for deposition and etching as described herein. Or, as described below, the EUVL patterning tool may be a module on a larger multi-component tool. Figure 9 illustrates a semiconductor process cluster tool architecture having a vacuum integrated deposition, EUV patterning, and dry develop / etch module interfaced with a vacuum transfer module suitable for carrying out the processes described herein. Although the processes can be carried out without such vacuum integrated equipment, such equipment may be advantageous in some embodiments.

[0368] FIG. 9 illustrates a semiconductor process cluster tool architecture having a vacuum integrated deposition and patterning module interfaced with a vacuum transfer module suitable for carrying out the processes described herein. The arrangement of transfer modules to "transfer" wafers between multiple storage facilities and processing modules is sometimes referred to as a "cluster tool architecture" system. The deposition and patterning modules are vacuum integrated according to the requirements of a particular process. Other modules, such as for etching, can also be included in the cluster.

[0369] A vacuum transport module (VTM) 938 interfaces with four processing modules 920a-920d, which can be individually optimized to perform various fabrication processes. By way of example, processing modules 920a-920d can be implemented to perform deposition, evaporation, ELD, dry develop, etch, strip, and / or other semiconductor processes. For example, module 920a can be an ALD reactor that can be operated to perform non-plasma thermal atomic layer deposition as described herein, such as a Vector tool available from Lam Research, Inc., Fremont, Calif., and module 920b can be a PECVD tool, such as a Lam Vector®. It should be understood that the figures are not necessarily drawn to scale.

[0370] Airlocks 942 and 946, also known as loadlocks or transfer modules, interface with the VTM 938 and the patterning module 940. For example, as mentioned above, a suitable patterning module could be a TWINSCAN NXE:3300B® platform supplied by ASML, Veldhoven, The Netherlands). This tool architecture allows workpieces such as semiconductor substrates or wafers to be transferred under vacuum so that they do not react before exposure. The integration of the deposition module with the lithography tool is facilitated by the fact that EUVL also requires a significantly reduced pressure, given the strong optical absorption of incident photons by ambient gases such as H2O, O2, etc.

[0371] As mentioned above, this integrated architecture is only one possible embodiment of a tool for carrying out the described process. The process can also be carried out with more conventional standalone EUVL scanners and as a module, a deposition reactor such as the Lam Vector tool described with reference to FIG. 9 but without an integrated patterning module, either standalone or integrated in a cluster architecture with other tools such as etch, strip, etc. (e.g., Lam Kiyo or Gamma tools).

[0372] Airlock 942 may be an "out" load lock, referring to the transfer of substrates from the VTM 938 servicing deposition module 920a to the patterning module 940, and airlock 946 may be an "in" load lock, referring to the transfer of substrates from the patterning module 940 back to the VTM 938. The in load lock 946 may also provide an interface to the outside of the tool for access and egress of substrates. Each process module has a facet that interfaces the module to the VTM 938. For example, deposition process module 920a has facet 936. Within each facet, sensors, such as sensors 1-18 shown, are used to detect the passage of wafer 926 as it moves between the respective stations. Patterning module 940 and airlocks 942 and 946 may similarly include additional facets and sensors not shown.

[0373] The main VTM robot 922 transfers wafers 926 between modules including airlocks 942 and 946. In one embodiment, the robot 922 has one arm, and in another embodiment, the robot 922 has two arms, each arm having an end effector 924 that lifts a wafer such as wafer 926 for transfer. A front-end robot 944 is used therein to transfer wafers 926 from the exit airlock 942 to the patterning module 940 and from the patterning module 940 to the entry airlock 946. The front-end robot 944 can also transfer wafers 926 between the entry loadlock and the exterior of the tool for substrate access and egress. Because the entry airlock module 946 has the ability to adapt the environment between atmospheric pressure and vacuum, the wafers 926 can move between the two pressure environments without being damaged.

[0374] It should be noted that the EUVL tool operates at a higher vacuum than the deposition tool. In this case, it is desirable to increase the vacuum environment of the substrate during transfer between the deposition tool and the EUVL tool to allow for outgassing of the substrate before entering the patterning tool. The unloading airlock 942 can provide this function by holding the transferred wafer at a low pressure, no higher than the pressure in the patterning module 940 for a period of time, and venting the off-gassing, so that the optics of the patterning tool 940 are not contaminated by off-gassing from the substrate. A suitable pressure for the venting off-gas airlock is 1E-8 Torr or less.

[0375] In some embodiments, a system controller (which may include one or more physical or logical controllers) controls some or all of the operations of the cluster tool and / or its separate modules. Note that the controller may be local to the cluster architecture, or may be located outside the cluster architecture on the manufacturing floor, or may be located at a remote location and connected to the cluster architecture via a network. The system controller 950 may include one or more memory devices and one or more processors. The processor may include a central processing unit (CPU) or computer, analog and / or digital input / output connections, stepper motor controller boards, and other similar components. Instructions are executed on the processor to perform appropriate control operations. These instructions may be stored in a memory device associated with the controller or provided over a network. In certain embodiments, the system controller executes system control software.

[0376] The system control software may include instructions for controlling the timing of application and / or magnitude of any aspect of tool or module operation. The system control software may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be written to control the operation of process tool components necessary to perform various process tool processes. The system control software may be coded in any suitable computer readable programming language. In some embodiments, the system control software includes input / output control (IOC) sequence instructions for controlling the various parameters described above. For example, each stage of a semiconductor fabrication process may include one or more instructions executed by the system controller. For example, instructions for setting process conditions for condensation, deposition, evaporation, patterning, and / or etching stages may be included in the corresponding recipe stages.

[0377] It should be noted that the computer controlling the movement of the wafers may be local to the cluster architecture, or may be located outside the cluster architecture on the manufacturing floor, or may be located at a remote location and connected to the cluster architecture via a network. The controllers described above with respect to any of Figures 6, 7, 8, or 10 may be implemented using the tool of Figure 9.

[0378] FIG. 10 shows an example of a deposition chamber (e.g., for vapor-based deposition of a film). As can be seen, an apparatus 1000 is shown having a processing chamber 1002 including a lid 1008. The processing chamber 1002 may include a wafer transfer passage 1004 through one of the walls of the processing chamber 1002, the wafer transfer passage 1004 being sized to allow a substrate 1022 to pass through and enter the interior of the processing chamber 1002, where the substrate 1022 may be placed on a substrate support 1024. The wafer transfer passage 1004 may have a gate valve 1006 or similar door mechanism operable to seal or open the wafer transfer passage, thereby isolating the environment within the processing chamber 1002 from the environment on the other side of the gate valve 1006. For example, the processing chamber 1002 may be provided with a substrate 1022 via a wafer handling robot located in an adjacent transfer chamber. Such a transfer chamber may, for example, have multiple processing chambers 1002 arranged around its periphery, with each such processing chamber 1002 connected to the transfer chamber via a corresponding gate valve 1006 .

[0379] The wafer support 1024 may include, for example, an electrostatic chuck (ESC) 1026 that may be used to provide a wafer support surface for supporting the substrate 1022. The ESC 1026 may include, for example, a base plate 1034 bonded to a top plate 1028 that rests on the base plate 1034. The top plate 1028 may be made of, for example, a ceramic material and may have several other components embedded therein. In the illustrated example, the top plate 1028 has two separate electrical systems embedded therein. One such system is an electrostatic clamping electrode system, which may have one or more clamping electrodes 1032 that may be used to generate an electric charge in the substrate 1022, such that the substrate 1022 is attracted against the wafer support surface of the top plate 1028. While in the embodiment of FIG. 10 there are two clamping electrodes 1032 providing a bipolar electrostatic clamping system, in some embodiments only a single clamping electrode 1032 may be used to provide a monopolar electrostatic clamping system.

[0380] Another system is a thermal control system that can be used to control the temperature of the substrate 1022 during processing conditions. In FIG. 10, the thermal control system is a multi-zone thermal control system featuring four annular resistive heater traces 1030a, 1030b, 1030c, and 1030d that are concentric with one another and located beneath a clamping electrode 1032. The central resistive heater trace 1030a may fill a generally circular area in some implementations, and each resistive heater trace 1030a / b / c / d may follow a generally serpentine or other serpentine path within a corresponding annular region. Each resistive heater trace 1030a / b / c / d may be individually controlled to provide a variety of radial heating profiles to the top plate 1028, and such a four-zone heating system may be controlled to maintain the substrate 1022, for example, with a temperature uniformity of ±0.5° C. in some cases. Although the apparatus 1000 of FIG. 10 features a four-zone heating system within the ESC 1026, in other embodiments, a single-zone or multi-zone heating system having more or less than four zones may be used.

[0381] For example, in some implementations of the temperature control mechanisms described above, a heat pump may be used in place of the resistive heating traces. For example, in some implementations, the resistive heater traces may be replaced or augmented by Peltier junctions or other similar devices that can be controlled to "pump" heat from one side of the top plate 1028 to the other. Such a mechanism may be used, for example, to draw heat from the top plate 1028 (and thus the substrate 1022) and direct the heat to the base plate 1034 and heat exchange passages 1036, thereby allowing the substrate 1022 to be cooled more quickly and more effectively, as desired.

[0382] The ESC 1026 may also include a base plate 1034, which may be used, for example, to provide structural support to the underside of the top plate 1028 and may also act as a heat distribution system. For example, the base plate 1034 may include one or more heat exchange passages 1036 disposed generally distributed throughout the base plate 1034, for example, the heat exchange passages 1036 may follow a serpentine, circular switchback, or spiral pattern around the center of the base plate 1034. During use, a heat exchange medium, for example, water or an inert fluorinated liquid, may be circulated through the heat exchange passages 1036. The flow rate and temperature of the heat exchange medium may be externally controlled to result in specific heating or cooling behavior within the base plate 1034.

[0383] The ESC 1026 may be supported by, for example, a wafer support housing 1042 connected to and supported by a wafer support column 1044. The wafer support column 1044 may have other passages, for example, wire passages 1048 for routing cabling, fluid flow conduits, and other equipment to the underside of the base plate 1034 and / or top plate 1028. For example, although not shown in FIG. 10, cabling for providing power to the resistive heater traces 1030a / b / c / d may be routed through the wire passages 1048, as may cabling for providing power to the clamp electrodes 1032. Other cables, for example, cables for temperature sensors, may also be routed through the wire passages 1048 to locations internal to the wafer support 1024. In embodiments having a temperature controllable base plate 1034, conduits for transporting heat exchange medium between the base plates 1034 may also be routed through the wire passages 1048. To avoid undue clutter, such cables and conduits are not shown in FIG. 10, but it should be understood that they are still present.

[0384] 10 also includes a substrate support Z actuator 1046 that can provide movable support to the wafer support column 1044. The wafer support Z actuator 1046 can be actuated to move the wafer support column 1044, and the wafer support 1024 supported thereby, vertically up or down, for example, by up to several inches, within the reaction volume 1020 of the processing chamber 1002. In doing so, the gap distance X between the substrate 1022 and the underside of the showerhead 1010 can be adjusted in response to various process conditions.

[0385] The wafer support 1024 may also include one or more edge rings, which in some implementations may be used to control and / or fine-tune various process conditions. In Figure 10, for example, an upper edge ring 1038 is provided that sits above lower edge rings 1040a and 1040b, which are supported by a wafer support housing 1042 and a third lower edge ring 1040c. The upper edge ring 1038, for example, may generally be exposed to the same processing environment as the substrate 1022, while the lower edge rings 1040a / b / c may generally be shielded from the processing environment. Due to the increased exposure of the upper edge ring 1038, the upper edge ring 1038 may have a limited life span and require more frequent replacement or cleaning compared to the lower edge rings 1040a / b / c.

[0386] The apparatus 1000 may also include a system for removing process gases from the processing chamber 1002 during and after processing. For example, the processing chamber 1002 may include an annular plenum 1056 that surrounds the wafer support column 1044. The annular plenum 1056 may in turn be fluidly connected to a vacuum foreline 1052 that may be connected to a vacuum pump, for example, such as may be located below a subfloor below the apparatus 1000. A regulator valve 1054 may be provided between the vacuum foreline 1052 and the processing chamber 1002 and may be actuated to control flow to the vacuum foreline 1052. In some implementations, a baffle 1050, e.g., an annular plate or other structure, may be provided that may serve to more evenly distribute the flow into the annular plenum 1056 around the wafer support column 1044, reducing the possibility of flow non-uniformities in the reactants flowing across the substrate 1022.

[0387] The showerhead 1010 is a dual plenum showerhead 1010 as shown, including a first plenum 1012 to which process gas is supplied via a first inlet 1016 and a second plenum 1014 to which process gas is supplied via a second inlet 1018. Typically, two plenums can be used to maintain separation between the precursors and the counter reactant prior to release of the precursors and the counter reactant. The showerhead 1010 may have three or more plenums in some implementations. In some cases, a single plenum is used to deliver the precursors to the reaction space 1020 of the processing chamber 1002. Each plenum may have a corresponding set of gas distribution ports that fluidly connect the respective plenum to the reaction space 1020 through the faceplate of the showerhead 1010 (the faceplate is the portion of the showerhead 1010 that is interposed between the bottom plenum and the reaction space 1020).

[0388] The first inlet 1016 and the second inlet 1018 of the showerhead 1010 can be supplied with process gases via a gas supply system, which can be configured to provide one or more precursors and / or reverse reactants as previously described herein. The illustrated apparatus 1000 is configured to provide multiple precursors and multiple reverse reactants. For example, a first valve manifold 1068a can be configured to supply a precursor to the first inlet 1016, while a second valve manifold 1068b can be configured to supply other precursors or other reverse reactants to the second inlet 1018.

[0389] A first valve manifold 1068a may be configured to supply one or more precursors to a first inlet 1016, while a second valve manifold 1068b may be configured to supply other precursors or other reactants to a second inlet 1018. In this example, the first valve manifold 1068a includes, for example, multiple valves A1-A5. Valve A2 may be, for example, a three-way valve having one port fluidly connected to a first vaporizer 1072a, another port fluidly connected to a bypass line 1070a, and a third port fluidly connected to a port on another three-way valve A3. Similarly, valve A4 may be another three-way valve having one port fluidly connected to a second vaporizer 1072b, another port fluidly connected to a bypass line 1070a, and a third port fluidly connected to a port on another three-way valve A5. One of the other ports on valve A5 may be fluidly connected to the first inlet 1016, and the remaining port on valve A5 may be fluidly connected to one of the remaining ports on valve A3. The remaining port on valve A3 may then be fluidly connected to valve A1, which may be fluidly interposed between valve A3 and a purge gas source 1074, e.g., a source of nitrogen, argon, or other suitable inert gas (for the precursor and / or back reactant). In some embodiments, only the first valve manifold is used.

[0390] For purposes of this disclosure, the term "fluidically connected" is used in reference to volumes, plenums, holes, etc. that may be connected to one another to form a fluid connection, similar to the way the term "electrically connected" is used in reference to components that are connected to one another to form an electrical connection. The term "fluidically interposed," when used, may be used to refer to a component, volume, plenum, or hole that is fluidly connected to at least two other components, volumes, plenums, or holes, such that fluid flowing from one of those other components, volumes, plenums, or holes to the other or another of those components, volumes, plenums, or holes will first flow through the "fluidically interposed" component before reaching the other or another of those components, volumes, plenums, or holes. For example, if a pump is fluidly interposed between a reservoir and an outlet, fluid flowing from the reservoir to the outlet will first flow through the pump before reaching the outlet.

[0391] The first valve manifold 1068a can be controllable to, for example, flow vapor from one or both of the vaporizers 1072a and 1072b to the processing chamber 1002 or through a first bypass line 1070a to the vacuum foreline 1052. The first valve manifold 1068a can also be controllable to flow purge gas from a purge gas source 1074 to the first inlet 1016.

[0392] For example, to flow vapor from the first vaporizer 1072a to the reaction space 1020, the valve A2 can be actuated to flow the vapor from the first vaporizer 1072a initially to the first bypass line 1070a. This flow can be maintained for a sufficient period of time for the flow of vapor to reach a steady state flow condition. After a sufficient time has passed (or after a flow meter (if used) indicates that the flow rate is stable), the valves A2, A3, and A5 can be actuated to direct the vapor flow from the first vaporizer 1072a to the first inlet. Similar operations with the valves A4 and A5 can be performed to deliver the vapor from the second vaporizer 1072b to the first inlet 1016. In some cases, it may be desirable to purge one of the vapors from the first plenum 1012 by actuating the valves A1, A3, and A5 to flow the purge gas from the purge gas source 1074 to the first inlet 1016. In some additional embodiments, it may be desirable to simultaneously flow vapor from one of the vaporizers 1072a or 1072b in parallel with flowing gas from the purge gas into the first inlet 1016. Such an embodiment may be used to dilute the concentration of reactants contained in such vapor.

[0393] It will be appreciated that the second valve manifold 1068b can be controlled in a similar manner, for example by controlling valves B1-B5, to supply vapor from the vaporizers 1072c and 1072d to the second inlet 1018 or to the second bypass line 1070b. It will further be appreciated that different manifold arrangements can be utilized as well, including a single integral manifold that includes valves to control the flow of precursors, counter reactants, and other reactants to the first inlet 1016 and second inlet 1018.

[0394] As previously mentioned, some devices 1000 may feature a fewer number of vapor sources, e.g., only two vaporizers 1072, in which case the valve manifold 1068 may be modified to have a fewer number of valves, e.g., only valves A1-A3.

[0395] As described above, an apparatus such as the apparatus 1000 that may be used to perform dry deposition of a film may be configured to maintain a particular temperature profile within the process chamber 1002. In particular, such an apparatus 1000 may be configured to maintain the substrate 1022 at a lower temperature, e.g., at least 25° C. to 50° C. lower, than most of the equipment of the apparatus 1002 that is in direct contact with the precursors and / or reverse reactants. In addition, the temperature of the equipment of the apparatus 1000 that is in direct contact with the precursors and / or reverse reactants may be kept at an elevated level that is high enough to prevent condensation of vaporized reactants on the surfaces of such equipment. At the same time, the temperature of the substrate 1022 may be controlled to a level that promotes condensation, or at least deposition, of the reactants on the substrate 1022.

[0396] To provide such temperature control, various heating systems may be included in the apparatus 1000. For example, the process chamber 1002 may have a receptacle for receiving a cartridge heater 1058; for example, for a process chamber 1002 having a generally cylindrical interior volume but a square or rectangular exterior shape, vertical holes may be drilled in the four corners of the housing of the chamber 1002 to receive the cartridge heater 1058. In some implementations, the showerhead 1010 may be covered with a heater blanket 1060 that may be used to apply heat across the entire exposed top surface of the showerhead 1010 to keep the showerhead temperature high. It may also be beneficial to heat the various gas lines used to direct vaporized reactants from the vaporizer 1072 to the showerhead 1010. For example, resistive heater tape may be wrapped around such gas lines and used to heat them to a high temperature. As shown in FIG. 10, all of the gas lines through which precursors and / or counter reactants may flow are shown as being heated, including the bypass line 1070. The only exceptions are the gas lines from the valve manifold 1068 to the first inlet 1016 and the second inlet 1018, which are very short and may be indirectly heated by the showerhead 1010. Of course, even these gas lines may be actively heated if desired. In some implementations, a heater may be provided in close proximity to the gate valve 1006 to provide heat to the gate valve as well.

[0397] The various operating systems of the apparatus 1000 can be controlled by a controller 1084, which can include one or more processors 1086 and one or more memory devices 1088 that are operatively connected to each other and communicatively connected to the various systems and subsystems of the apparatus 1000 to provide control functionality for these systems. For example, the controller 1084 can be configured to control valves A1-A5 and B1-B5, the various heaters 1058, 1060, the vaporizer 1072, the regulator valve 1054, the gate valve 1006, the wafer support Z actuator, etc.

[0398] Once the film layer is deposited on the substrate 1022, the substrate 1022 may be transferred to one or more subsequent processing chambers or tools for additional operations (e.g., any described herein), as described above. Additional deposition apparatus are described in International Patent Application No. PCT / US2020 / 038968, entitled "APPARATUS FOR PHOTORESIST DRY DEPOSITION," filed on June 22, 2020, and published as International Publication No. WO2020 / 263750, the disclosure of which is incorporated herein by reference in its entirety.

[0399] Embodiments of the present disclosure are directed to such processes and processing devices.

[0400] Working Example Example 1: Dry development of organotin tellurium (organoSn-Te) films using acid The present disclosure encompasses the use of dry development methods for highly absorbing metal-containing photoresists (PRs), such as bimetallic PRs containing Sn and Te. Compared to PRs containing tin oxide hydroxide, resist films containing additional highly absorbing metal elements (e.g., Te, Sb, Bi, and other elements described herein) can be incorporated to further improve EUV absorption and potentially lower lithography costs. In some cases, the incorporation of elements such as Te into the film can improve EUV absorption by up to 50% compared to a control film lacking Te.

[0401] Incorporating new elements can substantially change the material composition and properties of the PR, and additional development methods may be required. For example, while similar halide-based chemistries can etch bimetallic Sn-Te PR materials to some extent, the low volatility of Te-containing reaction products (e.g., halide tellurium compounds) and the etch selectivity between Sn and Te can pose additional challenges, especially at temperatures below room temperature. Such bimetallic resist materials can be developed using vapors of acid molecules (e.g., inorganic acids, organic acids, or other acids described herein) along with an oxygen-containing reactant. In one non-limiting example, dry development includes using a halogen-containing acid (e.g., HCl, HBr, HI, or trifluoroacetic acid) and O2 as the oxygen-containing reactant. In certain embodiments, mixing an oxygen-containing reactant with one or more etching gases can result in a more stable etch compared to an etching gas without the oxygen-containing reactant.

[0402] In addition to halogen-containing acids, development can include the use of molecules that can be decomposed or hydrolyzed to generate acid molecules, such as BCl3, which can selectively remove unexposed organic Sn-Te films to generate negative tone patterns.

[0403] In addition to inorganic acid molecules, organic acids can be used to selectively remove non-exposed regions. In some embodiments, the organic acids have a moderately high vapor pressure. Non-limiting organic acids include trifluoroacetic acid, formic acid, acetic acid, propionic acid, and other acids described herein (e.g., Table 1). In certain embodiments, the organic acids have a vapor pressure of about 1 Torr or greater at 25°C. [Table 1]

[0404] After development, additional operations can be performed to remove products formed as a result of exposure to acid. In one example, the further operations can include exposure to elevated temperatures (e.g., temperatures up to about 150° C., temperatures between about 0° C. and 200° C., between 0° C. and 175° C., or temperatures between 0° C. and 150° C., or temperatures described herein for bake operations). In another example, it can further include exposure to a hard bake operation, for example, at temperatures between about 0° C. and 300° C., between 0° C. and 250° C., or between 0° C. and 200° C. Without wishing to be limited by my mechanism, the elevated temperatures can be useful to vaporize reaction products formed from acid exposure in non-exposed areas. The reaction products can be any product resulting from a reaction between an element in the film and an atom from the acid. Non-limiting reaction products can include metal halides, where the film provides the metal and the acid is a halogen-containing acid providing the halogen. Examples of metal halides include MX2, MX3, or MX4, where M is a highly absorbing element (e.g., Te, In, Sn, Sb, and / or Bi) and X is a halogen. Metal halides can also include tellurium halides (e.g., TeCl2, TeBr2, TeI2, etc.). Another non-limiting reaction product can include a metal acetate, where the film provides the metal and the acid is an acetate-containing acid that provides the acetate.

[0405] In yet another example, the further operation can include exposure to a plasma. Without wishing to be limited by mechanism, the plasma can be used to remove residual species or other products formed as a result of the developing operation or exposure to acid. The plasma can be any chemical, inert gas, or reactive gas, such as hydrogen halides (e.g., HCl, HBr, HF, etc.) or other halogen-containing molecules (e.g., BCl3, CCl4, CCl5, CCl6, CCl7, CCl8, CCl9, CCl10, CCl11, CCl12, CCl13, CCl14, CCl15, CCl20, CCl35, CCl40, CCl50, CCl60, CCl70, CCl80, CCl90, CCl10, CCl15, CCl16, CCl17, CCl18, CCl19, CCl20, CCl21, CCl22, CCl23, CCl24, CCl25, CCl35, CCl36, CCl37, CCl38, CCl41, CCl42, CCl43, CCl44, CCl45, CCl46, CCl47, CCl48, CCl49, CCl50, CCl51, CCl52, CCl53, CCl54, CCl55, CCl56, CCl57, CCl58, CCl59, CCl60, CCl61, CCl62, CCl63, CCl64, CCl65, CCl65, CCl66, CCl67, CCl68, CCl69, CCl70, CCl71, CCl72, CCl73, CCl74, CCl75, CCl75, CCl76, CCl77, CCl78, CCl79, CCl79, CCl79, CCl79, CCl79, CCl79, CCl7 x F y , C x F y H z etc.).

[0406] In certain embodiments, the dry development strategy described herein can enable all dry processes (e.g., from deposition to development) for highly absorbing metal-containing resist materials (e.g., organic Sn—Te films).

[0407] Example 2: Wet development of organotin tellurium (organoSn-Te) films using acid The present disclosure encompasses the use of wet development methods for highly absorbing metal-containing photoresists (PRs), such as bimetallic PRs containing Sn and Te. Such bimetallic resist materials can be developed to produce negative tone patterns using acid solutions in different solvents or solvent mixtures. Both the acid concentration and the type of solvent / solvent mixture can affect the selectivity and etch rate and thus the exposure sensitivity of the resist.

[0408] In certain embodiments, acid solutions in different solvents or solvent mixtures can selectively remove unexposed resist material to produce negative tone patterns. In one embodiment, inorganic acids in solution are used, and this process has shown better selectivity and higher etch rates even at concentrations as low as 0.1% (v / v). Non-limiting inorganic acids include hydrogen halides (e.g., HCl, HBr, HI, and combinations thereof), phosphoric acid, sulfuric acid, and combinations thereof.

[0409] In other embodiments, an organic acid in solution is used. Non-limiting organic acids include formic acid, acetic acid, trifluoroacetic acid, and the like. Such organic acids can be used at any useful concentration, for example, greater than about 0.1% (v / v), or between about 0.1% (v / v) and 10% (v / v) acid in a solvent (e.g., an aqueous solvent such as water).

[0410] Any solvent may be used in the solution. In one embodiment, the solvent is an aqueous solvent, such as water. In another embodiment, the solvent is an organic solvent. Non-limiting organic solvents include alcohols (e.g., isopropyl alcohol (IPA)), ketones (e.g., 2-heptanone, acetone, etc.), ethers (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA)), esters (e.g., n-butyl acetate, γ-butyrolactone, or ethyl 3-ethoxypropionate (EEP)), and combinations thereof, which can be used as wet developers. The choice of solvent / solvent mixture can affect the selectivity and / or etch rate.

[0411] definition By "acid" is meant any molecule, ion, or compound capable of donating a proton or forming a covalent bond with an electron pair.

[0412] "Acyloxy" or "alkanoyloxy", as used interchangeably herein, refers to an acyl or alkanoyl group, as defined herein, attached to the parent molecular group through an oxy group. In certain embodiments, the alkanoyloxy is -OC(O)-Ak, where Ak is an alkyl group, as defined herein. In some embodiments, the unsubstituted alkanoyloxy is C 2-7 Alkanoyloxy groups. Exemplary alkanoyloxy groups include acetoxy.

[0413] "Alkenyl" refers to an optionally substituted C alkyl group having one or more double bonds. 2-24 An alkenyl group is a cyclic (e.g., C 3-24The alkenyl group may be cyclic, cycloalkenyl, or acyclic. The alkenyl group may also be substituted or unsubstituted. For example, the alkenyl group may be substituted with one or more of the substituents described herein for alkyl. Non-limiting unsubstituted alkenyl groups include allyl and vinyl. In some embodiments, the unsubstituted alkenyl group is C 2-6 , C 2-8 , C 2-10 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , C 2-24 , C 3-8 , C 3-10 , C 3-12 , C 3-16 , C 3-18 , C 3-20 , or C 3-24 It is an alkenyl group.

[0414] "Alkenylene" means a polyvalent (e.g., divalent) form of an alkenyl group, which is an optionally substituted C alkyl group having one or more double bonds. 2-24 An alkenylene group is a cyclic (e.g., C 3-24 The alkenylene group can be cyclic, cycloalkenyl, or acyclic. The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substituents described herein for alkyl. Exemplary non-limiting alkenylene groups include -CH=CH- or -CH=CHCH2-.

[0415] "Alkoxy" refers to -OR, where R is an optionally substituted alkyl group as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, trihaloalkoxy, such as trifluoromethoxy, and the like. An alkoxy group can be substituted or unsubstituted. For example, an alkoxy group can be substituted with one or more of the substituents described herein for alkyl. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C1-18 , C 1-20 , or C 1-24 Examples of the alkyl group include alkoxy groups.

[0416] The terms "alkyl" and "alk" refer to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), cyclopropyl, n-butyl (n-Bu), isobutyl (i-Bu), s-butyl (s-Bu), t-butyl (t-Bu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. An alkyl group can be cyclic (e.g., C 3-24 The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can include a haloalkyl, where the alkyl group is substituted with one or more halo groups as described herein. In another example, the alkyl group can be substituted with 1, 2, 3, or, in the case of an alkyl group of 2 or more carbons, 4 substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., -O-Ak, where Ak is an optionally substituted C 1-6 (2) amino (e.g., -NR N1 R N2 , R N1 and R N2 Each of is independently H or optionally substituted alkyl, or R N1 and R N2each taken together with the nitrogen atom to which it is attached forms a heterocyclyl group), (3) aryl, (4) arylalkoxy (e.g., -O-Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl), (5) aryloyl (e.g., -C(O)-Ar, where Ar is an optionally substituted aryl), (6) cyano (e.g., -CN), (7) carboxaldehyde (e.g., -C(O)H), (8) carboxyl (e.g., -COH), (9) C 3-8 Cycloalkyl (e.g., monovalent saturated or unsaturated non-aromatic cyclic C 3-8 (10) halo (e.g., F, Cl, Br, or I), (11) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms such as nitrogen, oxygen, phosphorus, sulfur, or halo, unless otherwise specified), (12) heterocyclyloxy (e.g., -O-Het, where Het is a heterocyclyl as described herein), (13) heterocyclyloyl (e.g., -C(O)-Het, where Het is a heterocyclyl as described herein), (14) hydroxyl (e.g., -OH), (15) N-protected amino, (16) nitro (e.g., -NO), (17) oxo (e.g., =O), (18) -COR A , R A (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c) (C 4-18 Aryl)C 1-6 (19) -C(O)NR B R C , R B and R C each of which is independently (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) (C 4-18 Aryl)C 1-6alkyl (e.g., -Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl), and (20) -NR G R H , R G and R H each of which is independently (a) hydrogen, (b) an N-protecting group, (c) C 1-6 Alkyl, (d) C 2-6 alkenyl (e.g., optionally substituted alkyl having one or more double bonds); 2-6 alkynyl (e.g., optionally substituted alkyl having one or more triple bonds); (f) C 4-18 Aryl, (g) (C 4-18 Aryl)C 1-6 alkyl (e.g., Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (h) C 3-8 cycloalkyl, and (i) (C 3-8 Cycloalkyl)C 1-6 alkyl (e.g., -Lk-Cy, where Lk is a divalent form of an optionally substituted alkyl group and Cy is an optionally substituted cycloalkyl as described herein), and in one embodiment, there are no two groups attached to the nitrogen atom via a carbonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is selected from the group consisting of C 1-3 , C 1-6 , C 1-8 , C 1-10 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-6 , C 2-8 , C 2-10 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , C 2-24 , C 3-8, C 3-10 , C 3-12 , C 3-16 , C 3-18 , C 3-20 , or C 3-24 It is an alkyl group.

[0417] "Alkylene" refers to the polyvalent (e.g., divalent) form of an alkyl group as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, an alkylene group is a C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 It is an alkylene group. The alkylene group can be branched or unbranched. The alkylene group can also be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more of the substituents described herein for alkyl.

[0418] "Alkynyl" refers to an optionally substituted C alkyl group having one or more triple bonds. 2-24 It refers to an alkyl group. Alkynyl groups can be cyclic or acyclic and are exemplified by ethynyl, 1-propynyl, and the like. Alkynyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more of the substituents described herein for alkyl. In some embodiments, an unsubstituted alkynyl group is a C 2-6 , C 2-8 , C 2-10 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , C 2-24 , C 3-8 , C 3-10 , C 3-12 , C 3-16 , C3-18 , C 3-20 , or C 3-24 It is an alkynyl group.

[0419] "Alkynylene" means a polyvalent (e.g., divalent) form of an alkynyl group, which is an optionally substituted C alkyl group having one or more triple bonds. 2-24 It is an alkyl group. An alkynylene group can be cyclic or non-cyclic. An alkynylene group can be substituted or unsubstituted. For example, an alkynylene group can be substituted with one or more of the substituents described herein for alkyl. Exemplary non-limiting alkynylene groups include -C≡C- or -C≡CCH2-.

[0420] "Amino" means -NR N1 R N2 means R N1 and R N2 is 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.

[0421] "Aryl" refers to fused benzo-C groups, such as, but not limited to, indanyl, tetrahydronaphthyl, and fluorenyl. 4-8It refers to groups that contain any carbon-based aromatic group, including phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, and the like, including cycloalkyl radicals (e.g., as defined herein). The term aryl also includes heteroaryl, which is defined as a group that contains an aromatic group with at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl, which is also included in the term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with 1, 2, 3, 4, or 5 substituents, such as those described herein for alkyl.

[0422] "Arylene" refers to a polyvalent (e.g., divalent) form of the aryl groups described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenylether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10 It is an arylene group. The arylene group can be branched or unbranched. The arylene group can also be substituted or unsubstituted. For example, the arylene group can be substituted with one or more of the substituents described herein for alkyl or aryl.

[0423] "(Aryl)(alkyl)ene" refers to a divalent form comprising an arylene group, as described herein, linked to an alkylene group or a heteroalkylene group, as described herein. In some embodiments, the (aryl)(alkyl)ene group is -L-Ar- or -L-Ar-L- or -Ar-L-, where Ar is an arylene group and each L is independently an optionally substituted alkylene group or an optionally substituted heteroalkylene group.

[0424] "Carbonyl" refers to the -C(O)- group, which can also be represented as >C=O, or CO group.

[0425] "Carboxyl" refers to the group -CO2H.

[0426] "Carboxylic acid" means an acid, as defined herein, having one or more carboxyl groups. Examples of carboxylic acids include monocarboxylic acids (having a single carboxyl group) or dicarboxylic acids (having two carboxyl groups).

[0427] "Carboxyalkyl" means an alkyl group, as defined herein, substituted with one or more carboxyl groups, as defined herein.

[0428] "Carboxyaryl" means an aryl group, as defined herein, substituted by one or more carboxyl groups, as defined herein.

[0429] "Cyclic anhydride" means, unless otherwise specified, a 3-, 4-, 5-, 6-, or 7-membered ring (e.g., 5-, 6-, or 7-membered ring) having a -C(O)-OC(O)- group in the ring. The term "cyclic anhydride" also includes bicyclic, tricyclic, and tetracyclic groups, any of the above rings being 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 heterocyclic ring. Exemplary cyclic anhydride groups include the radicals formed by removing one or more hydrogens from succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, isochroman-1,3-dione, oxepanedione, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, naphthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, and the like. Other exemplary cyclic anhydride groups include dioxotetrahydrofuranyl, dioxodihydroisobenzofuranyl, and the like. The cyclic anhydride groups can also be substituted or unsubstituted. For example, the cyclic anhydride groups can be substituted with one or more groups, including those described herein for heterocyclyl.

[0430] "Cycloalkenyl" means, unless otherwise specified, a monovalent unsaturated non-aromatic or aromatic cyclic hydrocarbon group of 3 to 8 carbons having one or more double bonds. Cycloalkenyl groups can also be substituted or unsubstituted. For example, cycloalkenyl groups can be substituted with one or more groups, including those described herein for alkyl.

[0431] "Cycloalkyl," unless otherwise specified, means a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group of three to eight carbons, exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.]heptyl, and the like. Cycloalkyl groups can also be substituted or unsubstituted. For example, cycloalkyl groups can be substituted with one or more groups, including those described herein for alkyl.

[0432] "Halo" means F, Cl, Br, or I.

[0433] "Haloalkenyl" means an alkenyl group, as defined herein, substituted with one or more halo.

[0434] "Haloalkyl" means an alkyl group, as defined herein, that is substituted with one or more halo.

[0435] "Haloalkynyl" means an alkynyl group, as defined herein, substituted with one or more halo.

[0436] "Haloaryl" means an aryl group, as defined herein, that is substituted with one or more halo.

[0437] "Heteroalkyl" means an alkyl group, as defined herein, that contains one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo).

[0438] "Heteroalkylene" refers to a divalent form of an alkyl group, as defined herein, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo). Heteroalkylene groups can be substituted or unsubstituted. For example, heteroalkylene groups can be substituted with one or more of the substituents described herein for alkyl.

[0439] "Heterocyclyl" means, unless otherwise specified, a 3-, 4-, 5-, 6-, or 7-membered ring (e.g., 5-, 6-, or 7-membered ring) containing 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo). The 3-membered ring has 0-1 double bonds, the 4- and 5-membered rings have 0-2 double bonds, and the 6- and 7-membered rings have 0-3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups, in which any of the above heterocycles are fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocycle such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, and the like. Heterocycles include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxanyl, benzodioxoc ...thiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benzisothiazolyl, benz zodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiazepinyl, benzoxathiocinyl, benzoxazepinyl,Benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytosinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diaziridinyl, dibenzoisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzooxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydropyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindol ... xanyl, dioxazinyl, dioxinyl, dioxiranyl, dioxenyl, dioxinyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl, indolinyl, indolizinyl, in dolyl (e.g., 1H-indolyl or 3H-indolyl), isathinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazolyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidinyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthyridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl, naphthyridinyl,Octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanoyl, oxetanyl, oxetyl, oxenyl, oxindolyl, oxiranyl, oxobenzisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzo) zothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyrronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolidizinyl, pyrrolyl (e.g., For example, 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (for example, 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenadinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothio Phenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianap...

Claims

1. 1. A method comprising: exposing a radiation-sensitive resist film to a patterning radiation source, thereby providing an exposed resist film having exposed and unexposed regions, said radiation-sensitive resist film comprising two or more elements having high patterning radiation absorption cross sections; developing the exposed radiation-sensitive resist film by removing the unexposed areas, thereby forming a pattern by a negative tone development process; Optionally processing the pattern; Equipped with The method comprises: carrying out said development in the presence of an organic acid; or performing said treating of said pattern in the presence of said organic acid; Equipped with method.

2. 10. The method of claim 1, The method further comprises carrying out the developing in the presence of the organic acid; said developing optionally further comprising delivering a vapor of an oxygen-containing reagent; (i) the developing comprises a dry development process comprising delivering a vapor of the organic acid or a vapor of a reactant configured to provide the organic acid to the exposed radiation-sensitive resist film; or (ii) The method, wherein said developing comprises a wet development process comprising delivering said organic acid in a solvent.

3. 3. The method of claim 2, The reactant is (i) Borane halides, such as trichloroborane (BCl 3 ), tribromoborane (BBr 3 ), triiodoborane (BI 3 ), halogenated silanes, tetrachlorosilane (SiCl 4 ), tetrabromosilane (SiBr 4 ), and tetraiodosilane (SiI 4 borane halides selected from the group consisting of (ii) Trialkylsilyl halides, such as trimethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl iodide, triethylsilyl chloride, triethylsilyl bromide, triethylsilyl iodide, tripropylsilyl chloride, tripropylsilyl bromide, tripropylsilyl iodide, triisopropylsilyl chloride, triisopropylsilyl bromide, triisopropylsilyl iodide, tributylsilyl chloride, tributylsilyl bromide, tributylsilyl iodide, triisobutylsilyl chloride, triisobutylsilyl bromide, triisobutylsilyl iodide, trisecbutylsilyl chloride, trisecbutylsilyl bromide, trisecbutylsilyl iodide, tritertbutylsilyl chloride, tritertbutylsilyl bromide, tritertbutylsilyl iodide, dimethyl-ethyl-silyl chloride, dimethyl- a trialkylsilyl halide selected from the group consisting of propylsilyl, dimethylisopropylsilyl chloride, dimethylbutylsilyl chloride, dimethylisobutylsilyl chloride, dimethylsecbutylsilyl chloride, dimethyltertbutylsilyl chloride, dimethyltertbutylsilyl bromide, dimethyltertbutylsilyl iodide, methyldiethylsilyl chloride, methyldiethylsilyl bromide, methyldiethylsilyl iodide, methyldipropylsilyl chloride, methyldiisopropylsilyl chloride, methyldibutylsilyl chloride, methyldiisobutylsilyl chloride, methyldisecbutylsilyl chloride, methylditertbutylsilyl chloride, methylbromideditertbutylsilyl, and methylditertbutylsilyl iodide, or (iii) Dialkyldihalosilanes, such as dimethyldichlorosilane, dimethyldibromosilane, dimethyldiiodosilane, diethyldichlorosilane, diethyldibromosilane, diethyldiiodosilane, dipropyldichlorosilane, dipropyldibromosilane, dipropyldiiodosilane, diisopropyldichlorosilane, diisopropyldibromosilane, diisopropyldiiodosilane, dibutyldichlorosilane, dibutyldibromosilane, dibutyldiiodosilane, diisobutyldichlorosilane, diisobutyldibromosilane, diisobutyldiiodosilane, disecbutyldichlorosilane, disecbutyldibromosilane, disecbutyldiiodosilane, the dialkyldihalosilane is selected from the group consisting of butyldiiodosilane, di-tertbutyldichlorosilane, di-tertbutyldibromosilane, di-tertbutyldiiodosilane, methyl-ethyl-dichlorosilane, methyl-ethyl-dibromosilane, methyl-ethyl-diiodosilane, methyl-propyl-dichlorosilane, methyl-isopropyl-dichlorosilane, methyl-butyl-dichlorosilane, methyl-isobutyl-dichlorosilane, methyl-secbutyl-dichlorosilane, methyl-tertbutyl-dichlorosilane, methyl-tertbutyl-dibromidosilane, and methyl-tertbutyl-diiodosilane.

4. 3. The method of claim 2, The method, wherein the organic acid is selected from the group consisting of formic acid, acetic acid, oxalic acid, citric acid, and trifluoroacetic acid, and optionally comprises a vapor pressure of at least about 15 Torr.

5. 3. The method of claim 2, The method, wherein the solvent is an aqueous solvent or an organic solvent, or the solvent comprises water, an alcohol, a ketone, an ether, an ester, or a combination thereof.

6. 10. The method of claim 1, A method wherein said developing occurs at a temperature ranging from about −10° C. to about 200° C. to remove volatile products present in said unexposed areas.

7. 10. The method of claim 1, After the development, Performing a plasma-based etching process and / or performing a post-development bake (PDB) The method further comprises:

8. 10. The method of claim 1, The method comprises carrying out the treating of the pattern in the presence of the organic acid, and the developing comprises the use of an acidic developer or the use of a vapor-based acidic etchant.

9. 9. The method of claim 8, The method, wherein the processing includes removing residual species including at least one of the two or more elements having the high patterning radiation absorption cross section.

10. 1. A method comprising: exposing a radiation-sensitive resist film to a patterning radiation source, thereby providing an exposed resist film having exposed and unexposed regions, said radiation-sensitive resist film comprising two or more elements having high patterning radiation absorption cross sections; developing the exposed radiation-sensitive resist film by removing the unexposed areas with acid, thereby forming a pattern by a negative tone dry development process; treating said pattern with a plasma-based etching process; A method comprising:

11. 11. The method of claim 10, The method wherein the developing comprises an oxygen-containing reagent.

12. 11. The method of claim 10, After the development, Performing a post-development bake (PDB) The method further comprises:

13. 11. The method of claim 10, (i) the radiation-sensitive resist film comprises an extreme ultraviolet (EUV)-sensitive photoresist layer or an EUV-sensitive inorganic photoresist layer; (ii) the radiation-sensitive resist film comprises tin (Sn), indium (In), bismuth (Bi), antimony (Sb), tellurium (Te), an oxide thereof, an alloy thereof, or a combination thereof; or (iii) The method, wherein the radiation-sensitive resist film comprises a chemical vapor deposition (CVD) film, a spin-on film, an organometallic oxide film, an organometallic oxide hydroxide film, a tin oxide film, or an organotin oxide film.

14. 11. The method of claim 10, Prior to said exposure, applying the radiation-sensitive resist film onto a surface of a substrate; Optionally, providing a radiation absorbing layer between the radiation sensitive resist film and the substrate. The method further comprises:

15. 11. The method of claim 10, Prior to said exposure, providing a radiation absorbing layer on a surface of a substrate; applying the radiation sensitive resist film on the surface of the radiation absorbing layer; The method further comprises:

16. 16. The method of claim 14 or 15, The coating is delivering one or more precursors to the surface of the substrate, wherein each precursor of the one or more precursors comprises a structure having formula (I) or (II): M a R b (I)、 M is a metal or atom with a high EUV absorption cross section; each R is independently H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, anionic ligand, neutral ligand, or multidentate ligand; a ≥ 1 and b ≥ 1, or - a 2 b L c (A) M is a metal or atom with a high EUV absorption cross section; each R is independently halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is independently a ligand, anionic ligand, neutral ligand, multidentate ligand, ion, or other moiety that reacts with a reverse reactant; R and L together with M can optionally form a heterocyclyl group, or R and L together can optionally form a heterocyclyl group; a ≥ 1, b ≥ 1, and c ≥ 1 A method comprising:

17. 16. The method of claim 14 or 15, The applying comprises providing one or more precursors, each precursor of the one or more precursors comprising: (i) InR 3 , R is independently halo, optionally substituted C 1-12 alkyl, or diketonate, and SnR 2 or SnR 4 , each R is independently halo, optionally substituted C 1-12 alkoxy, optionally substituted amino, optionally substituted aryl, cyclopentadienyl, or diketonate; (ii) BiR 3 , R is independently halo, optionally substituted C 1-12 Alkyl, mono-C 1-12 Alkylamino, di-C 1-12 alkylamino, optionally substituted aryl, optionally substituted bis(trialkylsilyl)amino, or diketonate; (iii) SbR 3 , each R is independently halo, optionally substituted C 1-12 Alkyl, optionally substituted C 1-12 alkoxy, or optionally substituted amino, and (iv) TeR 2 or TeR 4 , each R is independently halo, optionally substituted C 1-12 Alkyl, optionally substituted C 1-12 alkoxy, optionally substituted aryl, hydroxyl, oxo, or optionally substituted trialkylsilyl being selected from the group consisting of A method comprising:

18. 16. The method of claim 14 or 15, The coating is supplying a first precursor comprising tellurium (Te) and a second precursor comprising tin (Sn) to the surface of the substrate, wherein the first and second precursors are each supplied to the surface of the substrate in any order or simultaneously; A method comprising:

19. 16. The method of claim 14 or 15, providing the radiation absorbing layer includes providing a first precursor; applying the radiation-sensitive resist film includes providing a second precursor; the first precursor comprises a first atom having a high EUV absorption cross section, and the second precursor comprises a second atom having a high EUV absorption cross section, the first atom and the second atom being different; method.

20. 20. The method of claim 19, The method, wherein the first atoms include tellurium (Te), bismuth (Bi), indium (In), or antimony (Sb), and the second atoms comprise tin (Sn).

21. 1. An apparatus for processing a substrate, comprising: (a) one or more process chambers, each process chamber of said one or more process chambers optionally comprising a chuck or pedestal; (b) one or more inlets to said one or more process chambers and associated flow control hardware; (c) a controller having at least one processor and a memory, the at least one processor and the memory are communicatively coupled to each other; the at least one processor is at least operatively connected to the flow control hardware; The memory stores computer-executable instructions for controlling the at least one processor to cause a method according to any one of claims 1 to 20. Controller and An apparatus comprising:

22. The method of claim 1, The method wherein the organic acid is acetic acid.

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