Organometallic film for extreme ultraviolet patterning

Abstract

A method for processing a substrate comprises the steps of: exposing the substrate to a tin-containing precursor and exposing the substrate to an oxygen-containing precursor that reacts with tin from the tin-containing precursor to form a tin alkene oxide, thereby forming an extreme ultraviolet (EUV)-active photoresist film containing a tin alkene oxide component on a substrate disposed in a process chamber; and exposing the substrate to EUV light to pattern the EUV-active photoresist film.

Description

Technology Field

[0001] Cross-reference regarding related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 192,893 filed on May 25, 2021, and accordingly, that application is incorporated herein by reference.

[0003] The present invention relates to the field of semiconductor manufacturing and semiconductor devices, and more specifically, to a metalorganic film for EUV patterning. Background Technology

[0004] Generally, semiconductor devices such as integrated circuits (ICs) are manufactured by sequentially depositing and patterning layers of dielectric material, conductive material, and semiconductor material on a substrate to form a network of electronic components and interconnect elements (e.g., transistors, resistors, capacitors, metal lines, contacts, and vias) integrated in a monolithic structure.

[0005] Typically, photolithography is used to pattern thin films during semiconductor processes, in which photons are emitted from a light source onto a photosensitive photoresist to initiate a chemical reaction within the photoresist. Subsequently, the photoresist is developed, and exposed or unexposed portions of the photoresist are removed to form a pattern or mask. Extreme ultraviolet (EUV) radiation can be used to provide improved pattern resolution in advanced integrated circuits where feature size reduction is required. Conventional EUV photoresists are polymer-based chemically amplified resists (CARs) deposited on a substrate using liquid-based spin-on technology, which consumes a significant amount of composite precursors at a very high cost.

[0006] According to one embodiment of the present invention, a method for processing a substrate comprises the steps of: exposing the substrate to a tin-containing precursor and exposing the substrate to an oxygen-containing precursor that reacts with tin from the tin-containing precursor to form tin alkenoxide, thereby forming an extreme ultraviolet (EUV)-active photoresist film having a tin alkenoxide moiety on a substrate disposed in a process chamber; and exposing the substrate to EUV irradiation to pattern the EUV-active photoresist film.

[0007] According to one embodiment of the present invention, a method for processing a substrate comprises the steps of: exposing the substrate to a tin-containing precursor and exposing the substrate to an oxygen-containing precursor that reacts with tin from the tin-containing precursor to form a tin alkoxide, an aryloxide ligand, or a tin carboxylate, thereby forming an extreme ultraviolet (EUV)-active photoresist film comprising a tin alkoxide, a tin aryloxide, or a tin carboxylate component on a substrate disposed in a process chamber; and exposing the substrate to EUV light to pattern the EUV-active photoresist film.

[0008] According to one embodiment of the present invention, a method for forming an extreme ultraviolet (EUV)-active photoresist film on a substrate comprises the steps of: exposing the substrate to a tin-containing precursor; exposing the substrate to an oxygen-containing precursor to form an EUV-active photoresist film comprising tin and oxygen; and incorporating a photoacid generator (PAG) into the EUV-active photoresist film, wherein the incorporation step is performed during or after forming the EUV-active photoresist film. Brief explanation of the drawing

[0009] Now, for a more complete understanding of the present invention and its advantages, refer to the following description in conjunction with the accompanying drawings, and as the accompanying drawings: FIGS. 1a to 1d illustrate cross-sectional views of exemplary substrates during a manufacturing process in which EUV lithography patterning is subsequently performed after forming an organometallic film on a substrate, according to various embodiments, FIG. 1a illustrates an inlet substrate, FIG. 1b illustrates a substrate after depositing an organometallic film on the substrate, FIG. 1c illustrates a substrate after EUV exposure, and FIG. 1d illustrates a substrate after a development step; FIG. 2 illustrates an exemplary reaction of a metal-containing precursor and an oxygen-containing precursor for forming an organometallic film according to various embodiments; FIGS. 3 to 5 illustrate exemplary process systems for depositing an organometallic film on a substrate according to various embodiments, wherein FIG. 3 illustrates a process system for a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process according to one embodiment, FIG. 4 illustrates a plasma process system for a plasma-enhanced CVD (PECVD) or plasma-enhanced ALD (PEALD) process according to another embodiment, and FIG. 5 illustrates a liquid-based spin-on deposition system according to yet another embodiment; FIGS. 6a to 6c illustrate process flow diagrams of a method for forming an organometallic film on a substrate according to various embodiments, where FIG. 6a illustrates the process flow of some embodiments, FIG. 6b illustrates the process flow of an alternative embodiment, and FIG. 6c illustrates the process flow of yet another embodiment. Specific details for implementing the invention

[0010] Extreme ultraviolet (EUV) lithography can extend current photolithography technology beyond its optical limits by shifting to smaller imaging source wavelengths to pattern features of small critical dimensions. EUV light sources with a wavelength of approximately 13.5 nm can be used for state-of-the-art lithography tools, also referred to as scanners. Since EUV radiation is strongly absorbed in various solid materials and gases, the radiation path must be operated in a vacuum to prevent absorption by ambient gases such as H2O and O2.

[0011] Typically, EUV lithography uses an organic hard mask (e.g., an ashable hard mask of plasma-enhanced chemical vapor deposition (PECVD) amorphous carbon hydride) patterned using a conventional photoresist process. During photoresist exposure, EUV radiation is absorbed within the resist and the underlying substrate, generating high-energy photoelectrons (approx. 100 eV) and consequently a series of low-energy secondary electrons (approx. 10 eV) that diffuse laterally by several nanometers. These electrons increase the range of chemical reactions within the resist, which increases its EUV dose sensitivity. However, an inherently random pattern of secondary electrons is superimposed on the optical image. This unwanted secondary electron exposure causes a loss of resolution, observable line edge roughness (LER), and linewidth deviation within the patterned resist. These defects are repeated in the material to be patterned during subsequent pattern transfer etching.

[0012] Metal oxide materials (e.g., including tin (Sn) metal) have been identified as particularly suitable for direct EUV photopatterning as they strongly absorb EUV radiation. Unlike insulators such as conventional polymer-based chemical amplification resists (CARs), metal oxide materials are less susceptible to secondary electron exposure effects because secondary electrons can rapidly lose energy and become thermal neutronized as they are scattered through conduction electrons.

[0013] Embodiments of the present disclosure describe a method for depositing an organometallic film comprising tin (Sn) metal, wherein the organometallic film comprises a network of metal oxides and can be used as a photoresist for EUV patterning during the manufacture of an integrated circuit. The organometallic film may further comprise additional chemical elements such as halogens. According to one embodiment, the EUV-sensitive organometallic film may be vapor-deposited on a semiconductor substrate. According to another embodiment, the EUV-sensitive organometallic film may be deposited on a semiconductor substrate using liquid exposure. The organometallic film may then be patterned by EUV exposure under vacuum, and subsequently, an organometallic mask may be formed on the substrate by developing the pattern and removing exposed or unexposed portions of the organometallic film by a dry etching or wet etching process. The formed organometallic mask may then be used to pattern an underlying layer on the substrate by pattern transfer etching.

[0014] Preferably, the method described in this disclosure can enable a metal-containing EUV-sensitive photoresist having a higher EUV absorbance and consequently more suitable resist sensitivity compared to a conventional CAR. Depending on the higher EUV absorbance, the thickness of the photoresist required for acceptable performance can be reduced. Also preferably, the metal-containing EUV-sensitive photoresist described in this disclosure can exhibit better etching resistance than a conventional CAR after exposure and can exhibit a more uniform or homogeneous chemical composition than a CAR, both of which may be desirable for mitigating problems of blur or line edge roughness.

[0015] Hereinafter, steps of an exemplary manufacturing process, including the formation, patterning, and development of an organometallic film as an EUV-sensitive photoresist film, are first described with reference to FIGS. 1a through 1d. Next, an exemplary reaction for forming an organometallic film is illustrated in FIG. 2. Then, FIGS. 3 through 5 illustrate an exemplary process system for forming and depositing an organometallic film on a substrate. According to various embodiments, exemplary process flow diagrams are described with reference to FIGS. 6a through 6c. All drawings are illustrated for illustrative purposes only and are not illustrated in proportion.

[0016] FIGS. 1a to 1d illustrate cross-sectional views of an exemplary substrate (100) during a manufacturing process in which EUV lithography patterning is subsequently performed after forming an organometallic film on a substrate, according to various embodiments.

[0017] FIG. 1a illustrates a cross-sectional view of a substrate (100) to be patterned. For example, the substrate (100) may be a silicon wafer having a diameter of 150 mm, 200 mm, 300 mm, or 450 mm. In various embodiments, the substrate (100) may be part of a semiconductor device or may include a semiconductor device and may undergo a number of process steps according to a conventional process, for example. Accordingly, the substrate (100) may include a semiconductor layer useful in various microelectronic technologies. For example, a semiconductor structure may include a substrate (100) on which various device regions are formed.

[0018] In one or more embodiments, the substrate (100) may be a silicon wafer or a silicon-on-insulator (SOI) wafer. In certain embodiments, the substrate (100) may comprise silicon germanium, silicon carbide, gallium arsenide, gallium nitride, or other compound semiconductors. In other embodiments, the substrate (100) comprises a silicon-on-silicon layer or an SOI substrate, as well as heterogeneous layers such as silicon germanium-on-silicon, gallium nitride-on-silicon, and silicon carbon-on-silicon. In various embodiments, the substrate (100) is patterned or embedded within other components of a semiconductor device.

[0019] FIG. 1b shows a cross-sectional view of a substrate (100) after depositing an organometallic film (102) on the substrate (100).

[0020] As illustrated in FIG. 1b, an organometallic film (102) may be formed on the surface of a substrate (100) in one embodiment. In various embodiments, although not illustrated, the substrate (100) may further include various layers useful for manufacturing semiconductor devices, which may be collectively considered as part of the substrate (100) in this disclosure. For example, in certain embodiments, a dielectric layer comprising a silicon-based dielectric material having a low dielectric constant (i.e., a low-k value), such as an organosilicate glass (SiCOH), high-density SiCOH, porous SiCOH, and other porous dielectric materials, may be on the substrate (100). Additionally, a hard mask layer that can be patterned by a subsequent etching process after EUV photopatterning may be on the substrate (100). In various embodiments, the hard mask may comprise titanium nitride, titanium, titanium oxide, tantalum, tungsten carbide, other tungsten-based compounds, ruthenium-based compounds, or aluminum-based compounds. Additionally, the hard mask may be a carbon-based or silicon-based mask material. Additionally, the organometallic film (102) may be formed as part of a three-layer stack commonly used for photolithographic patterning. The three-layer stack may be used to create a pattern and transfer it to the hard mask, and then transfer it to a lower layer, such as a dielectric layer of the substrate (100), for example. In various embodiments, the three-layer stack may comprise a lower layer, an intermediate layer, and an organometallic film (102) as an EUV-sensitive photoresist. In one or more embodiments, the lower layer may comprise a carbon material and may be formed via a vapor deposition process such as CVD or a spin-on process. The intermediate layer may include silicon-based materials, including but not limited to spin-on glass (SOG), silicon carbide, silicon oxide, silicon oxycarbide, silicon oxynitride, silicon nitride, tin oxide, and a bottom anti-reflective coating film (BARC).Additionally, the intermediate layer (230) may be formed by vapor deposition such as CVD or a spin-on process. For illustrative purposes, FIGS. 1a through 1d only show an organometallic film (102) directly deposited on the substrate (100), but as described above, any suitable multilayer structure may be present as part of the substrate (100) in various embodiments.

[0021] In various embodiments, the organometallic film (102) may comprise tin (Sn). In certain embodiments, the organometallic film (102) may be a network of metal oxides comprising metal alkoxides, metal alkenoxides, metal aryl oxides, or metal carboxylate groups. These groups bonded to the metal are generally represented by the chemical formulas -OR, -OR', -OAr, and -OOCR, where R is an alkyl group, R' is an alkene group, and Ar is an aryl group. In various embodiments, the organometallic film (102) may be a polymer film and may not have a highly ordered structure such as a crystalline one. The number of functional groups bonded to the metal atoms may vary for each metal atom in the range of 1 to 4. The deposition of the organometallic film (102) may be performed by a dry or wet process. In various embodiments, the organometallic film (102) can be deposited by vapor deposition, for example, chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), atomic layer deposition (ALD), or plasma enhanced ALD (PEALD).

[0022] In a specific embodiment, the deposition process for the organometallic film (102) may include the step of exposing the substrate (100) to two precursors (i.e., a tin-containing precursor and an oxygen-containing precursor) within a process chamber. This exposure to the precursors may be performed stepwise or simultaneously. In various embodiments, the deposition process may be an ALD or pseudo-ALD process and may include two or more exposure steps. For example, the deposition process may be performed by first exposing the substrate (100) to a tin-containing precursor that forms an adsorption layer on the substrate (100), and then exposing the substrate (100) to an oxygen-containing precursor gas that reacts with the adsorbed tin-containing precursor. The exposure step may be repeated one or more times to increase the thickness of the organometallic film (102) on the substrate (100). In a specific embodiment, the exposure step may be separated temporally or spatially. Separating the exposure step temporally may be achieved by changing the gas composition within the process chamber. On the other hand, spatially separating the exposure step may be possible by using a plurality of spatially separated sections within the process chamber to transfer the substrate from one section to another. To more appropriately separate the exposure step in time, the vapor deposition may further include, between the exposure steps, a step of exhausting the process chamber, a step of purging, or both a step of exhausting and purging. These additional steps may be useful for ensuring that the reaction occurs only on the surface and not in the vapor phase. An ALD or pseudo-ALD method according to this embodiment may be particularly desirable for enabling layer-by-layer growth of an organometallic film (102) with high uniformity.

[0023] In another embodiment, instead of an ALD-type process, precursors may be supplied simultaneously into a process chamber to grow an organometallic film (102). This embodiment may be desirable as it enables continuous growth of the organometallic film (102) in a single step. In this embodiment, reactions between precursors may or may not occur as well as on the surface and in the gas phase.

[0024] In another embodiment, the organometallic film (102) may be deposited by liquid deposition using alternating exposures of a tin-containing precursor liquid and an oxygen-containing precursor liquid. Liquid deposition may further include a step of rinsing the substrate with a rinsing solution between exposure steps to remove excess and / or unreacted portions of the precursor. The rinsing solution may include deionized water, conventional organic solvents, such as acetone, propylene glycol monomethyl ether acetate, 1-methoxy-2-propanol, methyl isobutyl carbinol, hexane, tert-butanol, and isopropanol, or a mixture thereof. In another embodiment, the liquid precursors may be mixed first, and the mixed solution may be applied to the substrate to grow the organometallic film (102). In one or more embodiments, one of the precursors may be a gas and the other of the precursors may be a liquid, and accordingly, two different transfer modes (vapor and liquid) may be used to perform the deposition process.

[0025] In various embodiments, after forming an organometallic film (102) on a substrate (100), optional post-coating heat treatment may be performed to remove any excess solvent from the wet process, residual volatile by-products from the dry process, or both.

[0026] FIG. 1c shows a cross-sectional view of a substrate (100) after EUV exposure.

[0027] The method further includes the step of exposing the substrate (100) to an EUV light pattern (104), as schematically illustrated in FIG. 1c. The EUV light pattern (104) may be created using a photomask. In response to exposure to the EUV light pattern (104), a photoreaction may occur in the exposed region (105) of the organometallic film (102), while the unexposed region (107) remains unchanged. As a result of the photoreaction, the exposed region (105) may comprise a cross-linked organometallic film having material properties substantially different from those of the non-reactive portion of the organometallic film (102) (i.e., the unexposed region (107)). These differences in material properties include, in particular, volatility, reactivity, and / or solubility, which provide a source for tonality as a photoresist.

[0028] In one or more embodiments, as further described below, the organometallic film (102) may further include a light generator (PAG) that emits light in response to EUV exposure. The generated light may induce additional chemical reactions within the organometallic film (102), thereby improving tone.

[0029] Figure 1d shows a cross-sectional view of the substrate after the development step.

[0030] In FIG. 1d, the exposed area (105) is developed and removed by a dry etching or wet etching process to form a patterned organometallic mask comprising an opening (108) that exposes the underlying substrate (100) and an unexposed area (107). Typically, the photoresist can be removed by a wet process by treating the substrate with a developing solution to dissolve the reactive area (in the case of a positive tone resist) or the non-reactive area (in the case of a negative tone resist) of the photoresist. In various embodiments, a similar wet process may be applied for the development of the organometallic film (102). Alternatively, in other embodiments, a dry process may be used. The dry process may include, for example, an optional plasma etching process or a thermal process that preferably eliminates the use of a developing solution. In certain embodiments, the dry process may be performed using a reactive ion etching (RIE) process or an atomic layer etching (ALE). Afterward, the opening (108) can be used in an etching process to etch a shape portion within the substrate (100). In a specific embodiment, a dry process for forming and developing an organometallic film (102) can enable better nanoscale process control than a wet process, for example, to form a shape portion with a critical dimension of several nanometers or sub-nanometers.

[0031] In various embodiments, after EUV exposure (Fig. 1c) and before the development step (Fig. 1d), an optional post-exposure heat treatment (PEB) may be performed to further distinguish material properties between the exposed area (105) and the unexposed area (107). In certain embodiments, the PEB may be performed by heating the substrate (100) in a process chamber to a temperature of 70°C to 250°C, for example, 180°C to 225°C in one embodiment, under vacuum or under gas flow.

[0032] In the embodiment described above with reference to FIGS. 1a to 1d, the organometallic film (102) is a negative tone photoresist. In another embodiment, the organometallic film (102) may form a positive tone photoresist, and the exposed area (105) may be removed by a developing step, while the unexposed area (107) remains. In one embodiment, a positive tone photoresist may be made possible by performing additional chemical treatment, such as polymerization, to increase the etching resistance of the unexposed area (107) after EUV exposure, while the photoreaction within the exposed area (105) reduces the etching resistance.

[0033] FIG. 2 illustrates exemplary reactions of a metal-containing precursor and an oxygen-containing precursor for forming an organometallic film according to various embodiments.

[0034] The metal-containing precursor may comprise an organotin compound comprising a ligand represented by the general formula (SnL4) as shown in FIG. 2. In various embodiments, such ligands may comprise alkyl, amine, carboxylate, or halogen. In some embodiments, some ligands may comprise alkoxy groups. All four ligands may be the same in one embodiment, but different in another embodiment. An exemplary tin-containing precursor comprises trimethyltin chloride (Me3SnCl), dimethyltin dichloride (Me2SnCl2), methyltin trichloride (MeSnCl3), tris(dimethylamino)methyltin(IV)((CH3)2N)3SnMe, and (dimethylamino)trimethyltin(IV)((CH3)2N)SnMe3). In another embodiment, the tin-containing precursor may comprise four halogen ligands, for example, SnCl4 or SnI4. In various embodiments, a metal-containing precursor can be condensed with a co-reactant (e.g., an oxygen-containing precursor) to form an organometallic film (102).

[0035] As described in previous embodiments, an oxygen-containing precursor may be used as a co-reactant during the formation of an organometallic film. In various embodiments, the oxygen-containing precursor may preferably comprise a molecule having two or more reactive groups (e.g., a diol) that can crosslink more than two molecules of the metal-containing precursor and form a stable polymer structure on the substrate. In certain embodiments, by selecting a bulky structure of the reactive groups, steric hindrance can preferably be provided to each other, and excess condensation can be prevented prior to the EUV lithography process.

[0036] According to one embodiment, the oxygen-containing precursor may comprise an alkenol, and the deposited organometallic film may comprise a tin alkenoxide. An alkenol is a type of reactive structure or intermediate in organic chemistry represented by an alkene (olefin) in which at least one hydroxyl group is attached to one end of an alkene double bond. Depending on the use of an alkenol for the oxygen-containing precursor, a polymerizable structure may preferably be incorporated into the formed organometallic film, which may be desirable for improving the etching selectivity and the resulting toneability as an EUV-sensitive photoresist.

[0037] According to another embodiment, the oxygen-containing precursor may comprise an alcohol (e.g., methanol, ethanol, or isopropyl alcohol), a diol (e.g., ethylene glycol), or a polyol (e.g., glycerol), and the deposited organometallic may comprise a tin alkoxide. Additionally, an alkene-diol may be used, which may include but is not limited to 3,5-cyclohexadiene-1,2-diol, 2,5-cyclohexadiene-1,4-diol, 1,3-cyclohexadiene-1,4-diol, 1,3-butadiene-1,4-diol, cyclopenta-2,5-dien-1,2-diol, or (2Z,4E)-hepta-2,4-dien-2,6-diol.

[0038] According to another embodiment, the oxygen-containing precursor may comprise a phenolic compound, and the deposited organometallic film comprises a tin aryl oxide film. One embodiment of the phenolic compound comprises catechol, as shown in FIG. 2. Preferably, the two hydroxyl groups of the catechol may react with two different molecules of the tin-containing precursor so that each catechol monomer crosslinks the monomer of the tin oxide.

[0039] According to one embodiment, the oxygen-containing precursor may comprise a carboxylic acid, and the deposited organometallic film may comprise a tin carboxylate. In some embodiments, the oxygen-containing precursor may comprise an alkene component, and (a) at least one carboxylic acid group and at least one alcohol group or (b) two carboxylic acid groups.

[0040] According to one embodiment, additional polymerizable species may be incorporated into the organometallic film, and the additional polymerizable species react to form a polymer within the organometallic film. The degree of polymerization within the organometallic film during or after EUV exposure may be used to customize the subsequent etching properties of the organometallic film. Such modification of the organometallic film through additional polymerization, and the resulting change in etching properties, can preferably improve the tone of the organometallic film as an EUV-sensitive photoresist. For example, in the case of a negative tone resist, the exposed area of ​​the organometallic film must have a higher etching resistance than the unexposed area, and depending on the additional polymerization, the etching resistance of the exposed area may be further increased.

[0041] A portion of the organometallic film may be crosslinked by polymerizing the alkene portion of the organometallic film before, during, or after EUV exposure (e.g., before or after removing a portion of the film by a development step). In certain embodiments, crosslinking may be performed by chemically bonding two or more molecules within the organometallic film by covalent bonding, and by a Diels-Alder polymerization process, a radical polymerization process, and / or a cationic polymerization process. In one or more embodiments, such polymerization processes may include a step of exposing the substrate to a catalyst and may be performed in the presence of the catalyst.

[0042] Additionally, in certain embodiments, an organometallic film (102) may be formed using more than one type of metal-containing precursor and more than one type of oxygen-containing precursor. By using more than one type of metal-containing and / or oxygen-containing precursor, the overall physical and chemical properties (e.g., bulkiness, carbon-to-oxygen ratio, and / or hydrophobicity / hydrophilicity) of the resulting organometallic film (102) as an EUV-sensitive photoresist film may be finely tuned, preferably.

[0043] According to one embodiment, the method further comprises the step of incorporating a photo-generating agent (PAG) into an organometallic film prior to EUV exposure. Generally, incorporating a PAG into the photoresist results in enhanced sensitivity through chemical amplification. The PAG can emit a large number of photo molecules for every absorbed photon, and these photo molecules diffuse and react with protecting groups within the backbone of the photoresist.

[0044] In one embodiment, the incorporation of the PAG is achieved by first exposing a substrate to an aluminum (Al) precursor represented by the general chemical formula (AlL3), and then exposing the substrate to a fluorinated alcohol (e.g., CF3OH, etc.) precursor, so that an aluminum fluoroalkoxide component (e.g., Al(OCF3)) is used as the PAG. x This can be done by incorporating (etc.) into the organometallic film. Afterwards, the organometallic film is exposed to EUV radiation, which generates light from the aluminum fluoroalkoxide component to form a crosslink that polymerizes the exposed portion of the film.

[0045] In another embodiment, a substrate is first exposed to a boron (B) precursor represented by the general chemical formula (BL3), and then the substrate is exposed to a fluorinated alcohol precursor (e.g., CF3OH, etc.) or a fluorinated phenol precursor (e.g., C6F5OH, etc.) so that a boron fluoroalkoxide (e.g., B(OCF3)) is used as a PAG. x etc.) or boron fluorophenoxide (e.g., B(OC6F5) x The incorporation of PAG can be performed by incorporating (etc.) into the organometallic film. Afterwards, the organometallic film is exposed to EUV radiation that generates light from boron fluoroalkoxide or boron fluorophenoxide components to form a crosslink that polymerizes the exposed portion of the film.

[0046] FIG. 3 illustrates a process system for depositing an organometallic film on a substrate according to one embodiment.

[0047] FIG. 3 illustrates a process system (1) that may be configured to perform an ALD or CVD process. The process system (1) includes a process chamber (10) having a substrate holder (20) configured to support a substrate (22) on which an organometallic film is deposited. The process chamber (10) further includes an upper assembly (30) (e.g., a showerhead) coupled to a precursor supply system (40) configured to supply one or more tin-containing precursor gases. The precursor supply system (42) is configured to supply an oxygen-containing precursor gas. The oxygen-containing precursor gas may include, for example, an alkenol, an alcohol, a diol, a phenol, a carboxylic acid, or a combination thereof. The process system (1) further includes a purge gas supply system (44) and auxiliary gas supply systems (46, 48, and 50). The auxiliary gas supply system (46, 48, and 50) can be used, for example, to supply additional tin-containing precursor gas and oxygen-containing precursor gas into the process chamber (10).

[0048] Additionally, the process system (1) includes a substrate temperature control system (60) configured to be coupled to a substrate holder (20) to raise and control the temperature of a substrate (22). The substrate temperature control system (60) includes a temperature control element, such as a cooling system that receives heat from the substrate holder (20) and transfers heat to a heat exchanger system (not shown), or, when heating, transfers heat from the heat exchanger system. Additionally, the temperature control element may include a heating / cooling element, such as a resistive heating element or a thermoelectric heater / cooler, which may be included in the substrate holder (20), as well as in the chamber wall of the process chamber (10) and any other component within the process system (1). For example, the substrate temperature control system (60) may be configured to raise and control the substrate temperature from room temperature to about 350°C to about 550°C. Alternatively, the substrate temperature may be in the range, for example, about 150°C to about 350°C. However, it must be understood that the substrate temperature is selected based on the desired temperature to induce the deposition of a specific organometallic film on the surface of a given substrate.

[0049] Additionally, the process system (1) includes a controller (70) that can be coupled to the process chamber (10), a substrate holder (20), an upper assembly (30) configured to introduce process gas into the process chamber (10), a precursor supply system (40 and 42), a purge gas supply system (44), an auxiliary gas supply system (46, 48, and 50), and a substrate temperature control system (60). Alternatively or additionally, the controller (70) may be connected to one or more additional controllers / computers (not shown), and the controller (70) may obtain setting and / or configuration information from the additional controllers / computers.

[0050] In FIG. 3, singular process elements (10, 20, 30, 40, 42, 44, 46, 48, 50, and 60) are shown, but this is for illustrative purposes only, and the process system (1) may include any number of process elements, along with any number of controllers associated with them, in addition to independent process elements. A controller (70) may be used to configure any number of process elements (10, 20, 30, 40, 42, 44, 46, 48, 50, and 60), and the controller (70) may collect, provide, process, store, and display data from the process elements. The controller (70) may include a number of applications for controlling one or more process elements. For example, the controller (70) may include a graphical user interface (GUI) component (not shown) that can provide an easy-to-use interface that allows a user to monitor and / or control one or more process elements.

[0051] Referring again to FIG. 3, the process system (1) may be configured to process a 200 mm substrate, a 300 mm substrate, a 450 mm substrate, or a larger substrate. In fact, as understood by those skilled in the art, the process system (1) may be configured to process substrates, wafers, or LCDs regardless of their size. Accordingly, embodiments of the present disclosure are described primarily in relation to the processing of semiconductor substrates, but are not limited thereto. Alternatively, to deposit the organometallic film described in the embodiments of the present invention, a batch process system capable of processing a plurality of substrates simultaneously may be used.

[0052] In certain embodiments, a number of methods may be used to introduce tin-containing precursor gas and oxygen-containing precursor gas into the process chamber (10). One method includes the step of vaporizing the precursor using a separate bubbler or a direct liquid injection (DLI) system, or a combination thereof, and then mixing them in the gaseous phase before or within the process chamber (10). The DLI system has been proven to reduce the premature thermal decomposition of the precursor compared to the bubbling method. By individually controlling the vaporization rate of each precursor, the desired stoichiometry in the film being deposited can be achieved. Another method for delivering the first and second precursors includes the step of individually controlling two or more different liquid sources (pure precursor or precursor solution), and then mixing them before introducing them into a common vaporizer. This method may be used when the precursors are fused in solution or liquid form and have similar vaporization characteristics. Another method of delivering the first and second precursors includes the step of controlling the flow of a liquid precursor mixture (pure precursor or precursor solution) into a common vaporizer. Another method includes the use of a fusible mixed solid or liquid precursor within a bubbler. The liquid source precursor may include a pure liquid precursor, or a solid or liquid precursor dissolved in a fusible solvent. Possible fusible solvents include, but are not limited to, ionic liquids, hydrocarbons (aliphatic, olefin, and aromatic), amines, esters, glymes, crown ethers, ethers, and polyethers. In some cases, it may be possible to dissolve one or more fusible solid precursors in one or more fusible liquid precursors. It will be obvious to those skilled in the art that by controlling the relative concentration levels of the first and second precursors within a gas pulse, it is possible to deposit a film having a desired stoichiometry.

[0053] Referring again to FIG. 3, the purge gas supply system (44) is configured to introduce purge gas into the process chamber (10). For example, the introduction of purge gas may occur between the introduction of pulses of tin-containing precursor and oxygen-containing precursor gases into the process chamber (10). The purge gas may include an inert gas, for example, a noble gas (i.e., He, Ne, Ar, Kr, Xe), nitrogen (N2), or hydrogen (H2).

[0054] To improve heat transfer between the substrate (22) and the substrate holder (20), the substrate holder (20) may include a mechanical fastening system for attaching the substrate (22) to the upper surface of the substrate holder (20), or an electrical fastening system such as an electrostatic fastening system. Additionally, the substrate holder (20) may further include a substrate rear gas delivery system configured to introduce gas to the rear surface of the substrate (22) to improve gas-gap thermal conductivity between the substrate (22) and the substrate holder (20). Such a system may be used when temperature control of the substrate is required to be elevated or lowered. For example, the substrate rear gas system may include a two-zone gas distribution system, and the helium gas gap pressure may be varied individually between the center and the edge of the substrate (22).

[0055] As further illustrated in FIG. 3, the process chamber (10) is further coupled to a pressure control system (32) comprising a vacuum pumping system (34) and a valve (36) via a conduit (38), and the pressure control system (32) is configured to controllably exhaust the process chamber (10) to a pressure suitable for forming an organometallic film on a substrate (22) and for using tin-containing precursor and oxygen-containing precursor gases. The vacuum pumping system (34) may include a turbo molecular vacuum pump (TMP) or a cryogenic pump capable of a pumping speed of up to about 5,000 liters (or more) per second, and the valve (36) may include a gate valve for controlling the chamber pressure. Additionally, a device (not shown) for monitoring the chamber pressure may be coupled to the process chamber (10). The pressure control system (32) can be configured to control the process chamber pressure to about 0.1 Torr to about 100 Torr, for example, during the deposition of an organometallic film.

[0056] The precursor supply system (40 and 42), the purge gas supply system (44), and the auxiliary gas supply system (46, 48, and 50) may include one or more pressure control devices, one or more flow control devices, one or more filters, one or more valves, and / or one or more flow sensors. The flow control devices may include pneumatically driven valves, electromechanical (solenoid) valves, and / or high-speed pulsing gas injection valves. Gases may be pulsed into the process chamber (10) sequentially and alternately, and the length of each gas pulse may be, for example, about 0.1 seconds to about 100 seconds. Alternatively, the length of each gas pulse may be about 1 second to about 10 seconds. An exemplary gas pulse length for the precursor gas may be 0.3 to 3 seconds, for example, 1 second. An exemplary gas pulse length for the tin-containing precursor and oxygen-containing precursor gases may be 0.3 to 3 seconds, for example, 1 second. An exemplary purge gas pulse may be 1 to 20 seconds, for example, 3 seconds.

[0057] Referring further to FIG. 3, the controller (70) may include a digital I / O port, memory, and a microprocessor capable of generating a control voltage sufficient to not only monitor the output from the process system (1) but also to communicate and activate the input to the process system (1). Additionally, the controller (70) may be coupled to and exchange information with the process chamber (10), substrate holder (20), upper assembly (30), precursor supply system (40 and 42), purge gas supply system (44), auxiliary gas supply system (46, 48, and 50), substrate temperature control system (60), substrate temperature control system (60), and pressure control system (32). For example, a program stored in memory may be used to activate the input to the aforementioned components of the process system (1) according to a process method for performing a deposition process.

[0058] FIG. 4 illustrates a plasma process system for depositing an organometallic film on a substrate according to another embodiment.

[0059] FIG. 4 illustrates a plasma process system (2) that can be configured to perform not only an ALD or CVD process, but also a PEALD or PECVD process. The plasma process system (2) is similar to the process system (1) described in FIG. 3, but further includes a plasma generation system configured to generate plasma for at least a portion of the gas exposure within the process chamber (10). The plasma generation system includes a first power source (52) coupled to the process chamber (10) and configured to couple power to the gas introduced into the process chamber (10). The first power source (52) may be a variable power source and may include a radio frequency (RF) generator and an impedance matching network, and may further include an electrode through which RF power is coupled to the plasma of the process chamber (10). The electrode may be formed on an upper assembly (31) and may be configured to face the substrate holder (20). An impedance matching network can be configured to optimize the transfer of RF power from an RF generator to plasma by matching the input impedance of a process chamber containing electrodes and plasma with the output impedance of the matching network. For example, the impedance matching network serves to improve the transfer of RF power to the plasma of the process chamber (10) by reducing reflected power. Matching network topologies (e.g., L-type, π-type, T-type, etc.) and automatic control methods are well known to those skilled in the art.

[0060] Alternatively, the first power source (52) may include an RF generator and an impedance matching network, and may further include an antenna such as an inductive coil, thereby coupling RF power to the plasma of the process chamber (10). For example, the antenna may include a helical or solenoid coil, such as in an inductively coupled plasma source or a helicon source, or a flat coil, such as in a transformer-coupled plasma source.

[0061] Alternatively, the first power source (52) may include a microwave frequency generator and may further include a microwave antenna and a microwave window, thereby coupling microwave power to the plasma of the process chamber (10). The coupling of microwave power may be performed using electron cyclotron resonance (ECR) technology or surface wave plasma technology.

[0062] In a specific embodiment, the plasma process system (2) includes a substrate bias generation system configured to generate plasma (through a biased substrate holder) or assist in generating plasma during at least a portion of the alternating inflow of gas into the process chamber (10). The substrate bias system may include a substrate power supply (54) configured to be coupled to the process chamber (10) and to couple power to the substrate (22). The substrate power supply (54) may include an RF generator and an impedance matching network, and may further include electrodes through which RF power is coupled to the substrate (22). The electrodes may be formed on the substrate holder (20). For example, the substrate holder (20) may be electrically biased with an RF voltage by transmitting RF power from an RF generator (not shown) to the substrate holder (20) through an impedance matching network (not shown). Typical frequencies for RF bias may range from about 0.1 MHz to about 100 MHz and may be 13.56 MHz. RF bias systems for plasma processes are well known to those skilled in the art. Alternatively, RF power is applied to the substrate holder electrodes at multiple frequencies. Although the plasma generation system and the substrate bias system are shown as separate entities in FIG. 4, they may actually include one or more power sources coupled to the substrate holder (20).

[0063] Additionally, the plasma process system (2) includes a remote plasma system (56) for supplying a plasma excitation gas remotely before the plasma excitation gas exposed to the substrate (22) flows into the process chamber (10). The remote plasma system (56) may include, for example, a microwave frequency generator. The process chamber pressure may be about 0.1 Torr to about 10 Torr, or about 0.2 Torr to about 3 Torr.

[0064] FIG. 5 illustrates a spin-on deposition system according to another embodiment.

[0065] FIG. 5 schematically illustrates a process system (3) for processing a substrate according to another embodiment. The process system (3) may be a semi-closed spin-on deposition system similar to those currently used by the semiconductor industry to coat a substrate (wafer) with a photoresist layer. The semi-closed configuration enables fume control and minimizes the exhaust volume. The process system (3) includes a process chamber (310) comprising a substrate holder (312) for supporting, heating, and spinning a substrate (302), a rotation means (318) (e.g., a motor), and a liquid delivery nozzle (314) configured to supply a process liquid (316) to the upper surface of the substrate (302). A liquid supply system (304, 306, and 308) supplies different process liquids to the liquid delivery nozzle (314). For example, different process liquids may include a first liquid (e.g., a tin-containing precursor), a second reactant in a second liquid (e.g., an oxygen-containing precursor), and a washing liquid. According to another embodiment, the process system (300) may include an additional liquid delivery nozzle (not shown) for supplying different liquids to a substrate. An exemplary rotational speed may be about 500 rpm to about 1500 rpm, e.g. 1000 rpm, during exposure of the upper surface of the substrate (302) to the process liquid (316).

[0066] The process system (3) further comprises a controller (320) coupled to and capable of controlling a process chamber (310), a liquid supply system (304, 306 and 308), a liquid transfer nozzle (314), a rotating means (318), and a means for heating a substrate holder (312). The substrate (302) may be under an inert atmosphere during film deposition. The process system (300) may be configured to process a 200 mm substrate, a 300 mm substrate, or a larger size substrate. The process system (300) may be configured to process a substrate, a wafer, or an LCD, regardless of their size, as understood by those skilled in the art. Thus, although aspects of the invention are described in relation to the processing of semiconductor substrates, the invention is not limited thereto.

[0067] With reference to FIGS. 3 to 5, the process system described above is merely for illustrative purposes, and any other suitable system and configuration may be possible. For example, the plasma process system (2) of FIG. 4 may include a plurality of spatially separated sections within a process chamber (10), and a deposition process may be performed by moving a substrate through the spatially separated sections using a rotary stage.

[0068] FIGS. 6a to 6c illustrate process flow diagrams of a method for forming an EUV-active photolithography layer according to various embodiments. Since the process flow may follow the drawings described above (e.g., FIGS. 1a to 1c), it will not be described in detail again.

[0069] In FIG. 6a, the process flow (600) may begin with the formation of an EUV-sensitive photoresist film containing tin alkene oxide on a substrate within a process chamber (e.g., FIG. 1b) by first exposing the substrate to a tin-containing precursor (Block 610) and then exposing the substrate to an oxygen-containing precursor (Block 620). To enable the formation of tin alkene oxide, the oxygen-containing precursor may contain an alkenol. In various embodiments, the precursor may be a gas or a liquid, and accordingly, the exposing step may be a dry or wet process. In certain embodiments, between the exposing steps, an optional intermediate step for exhausting or purging the process chamber and / or cleaning the substrate may be performed (Block 615). With or without the optional intermediate step, the exposing step may be repeated to achieve a desired thickness of the EUV-sensitive photoresist film. When the exposure step is repeated as part of a periodic process, various process conditions (e.g., precursor supply rate, temperature, pressure, process time, etc.) for each step of each cycle may be the same in certain embodiments but may differ in other embodiments. In alternative embodiments, the exposure step may overlap wholly or partially in time, so the process may be more continuous rather than stepwise. Once an EUV-sensitive photoresist film is formed on a substrate, EUV lithography patterning may be performed by exposing the substrate to EUV light (Block 630, e.g., FIG. 1c). In one or more embodiments, an optional polymerization step may be performed before or after EUV exposure to induce additional polymerization within the EUV-sensitive photoresist film for enhanced tonality (Block 625). After EUV exposure, subsequent steps, such as a development step and a pattern transfer etching process, may be performed.

[0070] In FIG. 6b, the process flow (602) is essentially the same as the process flow (60), except that the oxygen-containing precursor may have a composition different from the previous embodiment for activating an EUV-sensitive photoresist film comprising a tin alkoxide, a tin aryl oxide, or a tin carboxylate.

[0071] In FIG. 6c, the process flow (604) can be initiated by first exposing the substrate to a tin-containing precursor (Block 610) and then exposing the substrate to an oxygen-containing precursor (Block 620). Additionally, after the EUV-sensitive photoresist film is formed, a step of incorporating a photo-generator (PAG) can be performed (Block 624). In various embodiments, the incorporation of PAG can be achieved by exposing the substrate to a PAG precursor, such as a pair of aluminum-containing or boron-containing precursors and a fluorinated alcohol precursor or a fluorinated phenol precursor. In certain embodiments, this step of incorporating PAG can be performed simultaneously during the formation of the EUV-sensitive photoresist film. Thus, the step of exposing the substrate to the PAG precursor (Block 624) may overlap wholly or partially with other exposing steps (Blocks 610 and 620) in time.

[0072] Exemplary embodiments of the present invention are summarized herein. Other embodiments may be understood from the entire specification as well as from the claims submitted herein.

[0073] Example 1. A method for processing a substrate, comprising the steps of: exposing the substrate to a tin-containing precursor and exposing the substrate to an oxygen-containing precursor that reacts with the tin from the tin-containing precursor to form a tin alkene oxide, thereby forming an extreme ultraviolet (EUV)-active photoresist film containing a tin alkene oxide component on the substrate disposed in a process chamber; and exposing the substrate to EUV rays to pattern the EUV-active photoresist film.

[0074] Example 2. The method of Example 1, wherein the tin-containing precursor and the oxygen-containing precursor are gases, and the method further comprises the step of exhausting or purging the process chamber between the exposure steps.

[0075] Example 3. In either Example 1 or 2, the tin-containing precursor and the oxygen-containing precursor are liquids, and the method further comprises the step of washing the substrate with a solvent to remove an excess amount of the tin-containing precursor or the oxygen-containing precursor between the exposure steps.

[0076] Example 4. The method of Example 1, wherein the exposing step overlaps in time.

[0077] Example 5. The method of Example 1, further comprising the step of repeating the exposing step.

[0078] Example 6. A method in any one of Examples 1 to 5, wherein the oxygen-containing precursor comprises an alkenol.

[0079] Example 7. A method in any one of Examples 1 to 6, wherein the tin-containing precursor comprises trimethyltin chloride (Me3SnCl), dimethyltin dichloride (Me2SnCl2), methyltin trichloride (MeSnCl3), tris(dimethylamino)methyltin(IV)((CH3)2N)3SnMe, or (dimethylamino)trimethyltin(IV)((CH3)2N)SnMe3.

[0080] Example 8. A method in any one of Examples 1 to 7, wherein the patterning step comprises the step of crosslinking the EUV-active photoresist film by polymerizing the alkene portion of the tin alkene oxide.

[0081] Example 9. A method in any one of Examples 1 to 8, wherein the crosslinking step is performed only in the EUV-exposed region of the EUV-active photoresist film during patterning of the EUV-active photoresist film through EUV lithography.

[0082] Example 10. A method for processing a substrate, comprising the steps of: exposing the substrate to a tin-containing precursor and exposing the substrate to an oxygen-containing precursor that reacts with the tin from the tin-containing precursor to form a tin alkoxide, a tin aryl oxide ligand, or a tin carboxylate, thereby forming an extreme ultraviolet (EUV)-active photoresist film comprising a tin alkoxide, a tin aryl oxide, or a tin carboxylate component on the substrate disposed in a process chamber; and exposing the substrate to EUV light to pattern the EUV-active photoresist film.

[0083] Example 11. Method according to Example 10, wherein the oxygen-containing precursor comprises alcohol.

[0084] Example 12. A method in which, in either Example 10 or 11, the oxygen-containing precursor comprises a diol.

[0085] Example 13. A method in any one of Examples 10 to 12, wherein the diol is ethylene glycol.

[0086] Example 14. A method in any one of Examples 10 to 13, wherein the EUV-active photoresist film comprises the tin aryl oxide and the oxygen-containing precursor comprises a phenol compound.

[0087] Example 15. A method in any one of Examples 10 to 14, wherein the EUV-active photoresist film comprises the tin carboxylate and the oxygen-containing precursor comprises a carboxylic acid.

[0088] Example 16. A method in any one of Examples 10 to 15, wherein the EUV-active photoresist film comprises the tin carboxylate, and the oxygen-containing precursor comprises an alkene component, a carboxyl group, and a hydroxyl group.

[0089] Example 17. A method in any one of Examples 10 to 16, wherein the EUV-active photoresist film comprises the tin carboxylate, and the oxygen-containing precursor comprises an alkene component and two carboxyl groups.

[0090] Example 18. A method for forming an extreme ultraviolet (EUV)-active photoresist film on a substrate, the method comprising: exposing the substrate to a tin-containing precursor; exposing the substrate to an oxygen-containing precursor to form the EUV-active photoresist film comprising tin and oxygen; and incorporating a photocatalytic generator (PAG) into the EUV-active photoresist film, wherein the incorporation step is performed during or after forming the EUV-active photoresist film.

[0091] Example 19. The method of Example 18, wherein the incorporation step comprises: exposing the substrate to an aluminum (Al) precursor; and exposing the substrate to a fluorinated alcohol precursor to incorporate the aluminum fluoroalkoxide component as the photocatalytic generator (PAG) into the EUV-active photoresist film.

[0092] Example 20. A method in which, in either Example 18 or 19, the incorporation step comprises: exposing the substrate to a boron (B) precursor; and exposing the substrate to a fluorinated alcohol precursor or a fluorinated phenol precursor to incorporate a boron fluoroalkoxide or boron fluorophenoxide component as the photocatalytic generator (PAG) into the EUV-active photoresist film.

[0093] Example 21. A substrate processing method comprising: providing a substrate in a process chamber; and exposing the substrate to a tin (Sn)-containing precursor that forms an adsorption layer on the substrate, and exposing the substrate to an oxygen-containing precursor that reacts with the adsorption layer, thereby forming an EUV-sensitive film on the substrate, wherein the oxygen-containing precursor comprises: a) an alkenol that reacts with the adsorption layer to form a tin alkene oxide film on the substrate; b) an alcohol that reacts with the adsorption layer to form a tin alkoxide film on the substrate; c) an alcohol that reacts with the adsorption layer to form a tin alkene oxide film on the substrate; d) a diol that reacts with the adsorption layer to form a tin alkoxide film on the substrate; e) a phenol that reacts with the adsorption layer to form a tin aryl oxide film on the substrate; and f) a carboxylic acid that reacts with the adsorption layer to form a tin carboxylate film on the substrate. or g) a substrate processing method comprising an alkene component and a) at least one carboxylic acid group and at least one alcohol group or b) two carboxylic acid groups for forming a tin carboxylate film on the substrate.

[0094] Example 22. The method of Example 21, wherein the tin-containing precursor and the oxygen-containing precursor are gases, and the method further comprises, between the exposure steps, a step of exhausting the process chamber, a step of purging, or both the step of exhausting and the step of purging.

[0095] Example 23. In either Example 21 or 22, the tin-containing precursor and the oxygen-containing precursor are liquids, and the method further comprises the step of washing the substrate between the exposure steps.

[0096] Example 24. A method comprising, in any one of Examples 21 to 23, further comprising the step of incorporating a light generator into the metal oxide film prior to EUV exposure.

[0097] Example 25. A method comprising, in any one of Examples 21 to 24, the step of exposing the substrate to an aluminum (Al) precursor and exposing the substrate to a fluorinated alcohol precursor to incorporate an aluminum fluoroalkoxide component into the metal oxide film; and the step of exposing the metal oxide film to EUV radiation to form a crosslink that polymerizes the exposed portion of the metal oxide film by generating a photon from the aluminum fluoroalkoxide component.

[0098] Example 26. A method further comprising the steps of: exposing the substrate to a boron (B) precursor and exposing the substrate to a fluorinated alcohol precursor or a fluorinated phenol precursor to incorporate a boron fluoroalkoxide or boron fluorophenoxide component into the metal oxide film; and exposing the metal oxide film to EUV radiation to form a crosslink that polymerizes the exposed portion of the metal oxide film by generating a photon from the boron fluoroalkoxide or boron fluorophenoxide component.

[0099] Example 27. A method in any one of Examples 21 to 26, wherein the tin-containing precursor comprises trimethyltin chloride (Me3SnCl), dimethyltin dichloride (Me2SnCl2), methyltin trichloride (MeSnCl3), tris(dimethylamino)methyltin(IV)((CH3)2N)3SnMe, and (dimethylamino)trimethyltin(IV)((CH3)2N)SnMe3.

[0100] Example 28. A method comprising, in any one of Examples 21 to 27, further the step of transferring the substrate to a lithography system for EUV exposure.

[0101] Although the present invention has been described with reference to exemplary embodiments, such description is not intended to be interpreted in a limiting sense. By referring to the description, various modifications and combinations of the exemplary embodiments, as well as other embodiments of the present invention, will be apparent to those skilled in the art. Accordingly, the appended claims are intended to include any such modifications or embodiments.

Claims

Claim 1 A method for processing a substrate, the method comprises the step of forming an extreme ultraviolet (EUV)-active photoresist film comprising a tin alkene oxide, a tin alkoxide, a tin aryl oxide, or a tin carboxylate component on the substrate disposed in a process chamber, wherein the forming step comprises the step of exposing the substrate to a tin-containing precursor, and the step of exposing the substrate to an oxygen-containing precursor that reacts with the tin from the tin-containing precursor to form a tin alkene oxide, a tin alkoxide, a tin aryl oxide, or a tin carboxylate, wherein the tin-containing precursor and the oxygen-containing precursor comprise a liquid; and the step of incorporating a photoacid generator (PAG) into the EUV-active photoresist film, wherein the photoacid generator (PAG) is formed from an aluminum (Al) precursor or a boron (B) precursor, and the photoacid generator (PAG) comprises an aluminum fluoroalkoxide component, a boron fluoroalkoxide component, or a boron fluorophenoxide component. A method for processing a substrate, comprising the steps of: a step of; and a step of patterning the EUV-active photoresist film by exposing the substrate to an EUV beam. Claim 2 A method for processing a substrate according to claim 1, wherein the step of exposing the substrate to the tin-containing precursor and the step of exposing the substrate to the oxygen-containing precursor are separated temporally by changing the precursor composition within the process chamber or separated spatially by using a plurality of separated sections within the process chamber. Claim 3 A method for treating a substrate according to claim 1, further comprising, between the step of exposing the substrate to the tin-containing precursor and the step of exposing the substrate to the oxygen-containing precursor, a step of washing the substrate with a solvent to remove an excess amount of the tin-containing precursor or the oxygen-containing precursor. Claim 4 A method for processing a substrate according to claim 1, wherein the step of exposing the substrate to the tin-containing precursor and the step of exposing the substrate to the oxygen-containing precursor overlap in time. Claim 5 A method for processing a substrate according to claim 1, further comprising the step of exposing the substrate to the tin-containing precursor and the step of exposing the substrate to the oxygen-containing precursor, wherein the exposure step is repeated. Claim 6 A method for treating a substrate according to claim 1, wherein the oxygen-containing precursor comprises an alkenol. Claim 7 A method for treating a substrate according to claim 1, wherein the tin-containing precursor comprises trimethyltin chloride (Me3SnCl), dimethyltin dichloride (Me2SnCl2), methyltin trichloride (MeSnCl3), tris(dimethylamino)methyltin(IV)((CH3)2N)3SnMe, or (dimethylamino)trimethyltin(IV)((CH3)2N)SnMe3. Claim 8 A method for treating a substrate according to claim 1, wherein the patterning step comprises the step of crosslinking the EUV-active photoresist film by polymerizing the alkene portion of the tin alkene oxide. Claim 9 A method for processing a substrate according to claim 8, wherein the crosslinking step is performed only in the EUV-exposed region of the EUV-active photoresist film during patterning of the EUV-active photoresist film through EUV lithography. Claim 10 A method for processing a substrate, wherein the method comprises the steps of: exposing the substrate to a tin-containing precursor; and exposing the substrate to an oxygen-containing precursor that reacts with the tin from the tin-containing precursor to form a tin alkene oxide, a tin alkoxide, a tin aryl oxide, or a tin carboxylate, thereby forming an extreme ultraviolet (EUV)-active photoresist film comprising the tin alkene oxide, the tin alkoxide, the tin aryl oxide, or the tin carboxylate component on the substrate disposed in a process chamber — the step of exposing the substrate to the tin-containing precursor and the step of exposing the substrate to the oxygen-containing precursor are temporally separated by changing the precursor composition in the process chamber or spatially separated by using a plurality of separated sections in the process chamber —; and the step of incorporating a photoacid generator (PAG) into the EUV-active photoresist film, wherein the photoacid generator (PAG) is formed of an aluminum (Al) precursor or a boron (B) precursor, and A method for processing a substrate, comprising: a step in which a photocatalytic generator (PAG) comprises an aluminum fluoroalkoxide component, a boron fluoroalkoxide component, or a boron fluorophenoxide component; and a step of patterning the EUV-active photoresist film by exposing the substrate to an EUV beam. Claim 11 In claim 10, a method for treating a substrate, wherein the oxygen-containing precursor comprises alcohol. Claim 12 In claim 10, a method for treating a substrate, wherein the oxygen-containing precursor comprises a diol. Claim 13 A method for treating a substrate according to claim 12, wherein the diol is ethylene glycol. Claim 14 A method for treating a substrate according to claim 10, wherein the EUV-active photoresist film comprises the tin aryl oxide, and the oxygen-containing precursor comprises a phenol compound. Claim 15 A method for treating a substrate according to claim 10, wherein the EUV-active photoresist film comprises the tin carboxylate, and the oxygen-containing precursor comprises a carboxylic acid. Claim 16 A method for treating a substrate according to claim 10, wherein the EUV-active photoresist film comprises the tin carboxylate, and the oxygen-containing precursor comprises an alkene component, a carboxyl group, and a hydroxyl group. Claim 17 A method for treating a substrate according to claim 10, wherein the EUV-active photoresist film comprises the tin carboxylate, and the oxygen-containing precursor comprises an alkene component and two carboxyl groups. Claim 18 A method for forming an extreme ultraviolet (EUV)-active photoresist film on a substrate, the method comprising: exposing the substrate to a tin-containing precursor; and exposing the substrate to an oxygen-containing precursor to form the EUV-active photoresist film comprising tin and oxygen. A method for forming an extreme ultraviolet (EUV)-active photoresist film on a substrate, comprising the steps of: exposing the substrate to an aluminum (Al) precursor or a boron (B) precursor; and exposing the substrate to a fluorinated alcohol precursor or a fluorinated phenol precursor to incorporate the photoacid generator (PAG) into the EUV-active photoresist film, wherein the incorporation step is performed during or after forming the EUV-active photoresist film. Claim 19 A method for forming an extreme ultraviolet (EUV)-active photoresist film on a substrate, wherein the incorporation step comprises: exposing the substrate to the aluminum (Al) precursor; and exposing the substrate to the fluorinated alcohol precursor to incorporate the aluminum fluoroalkoxide component as the photocatalytic generator (PAG) into the EUV-active photoresist film. Claim 20 A method for forming an extreme ultraviolet (EUV)-active photoresist film on a substrate, wherein the incorporation step comprises: exposing the substrate to the boron (B) precursor; and exposing the substrate to the fluorinated alcohol precursor or the fluorinated phenol precursor to incorporate a boron fluoroalkoxide or boron fluorophenoxide component as the photocatalytic generator (PAG) into the EUV-active photoresist film.

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