Metalorganic films for extreme ultraviolet patterning.

Abstract

A method for treating a substrate includes forming an extreme ultraviolet (EUV) active photoresist film containing a tin alkene oxide moiety on a substrate disposed in a process chamber by 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, and patterning the EUV active photoresist film by exposing the substrate to EUV radiation.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 192,893, filed May 25, 2021, which is incorporated herein by reference.

[0002] The present invention relates to the field of semiconductor manufacturing and semiconductor devices, and more particularly to organometallic films for EUV patterning. [Background technology]

[0003] Generally, semiconductor devices, such as integrated circuits (ICs), are fabricated by sequentially depositing and patterning layers of dielectric, conductive, and semiconducting materials on a substrate to form a network of monolithically integrated electronic components and interconnect elements (e.g., transistors, resistors, capacitors, metal lines, contacts, and vias).

[0004] Photolithography is commonly used to pattern thin films during semiconductor processing, where a light source emits photons onto a light-sensitive photoresist to initiate a chemical reaction in the photoresist. The photoresist is then 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 reduced feature sizes are required. A typical EUV photoresist is a polymer-based chemically amplified resist (CAR), which is deposited on a substrate using liquid-based spin-on techniques that consume significant amounts of precursor complexes at very high cost. Summary of the Invention [Means for solving the problem]

[0005] According to an embodiment of the invention, a method of treating a substrate includes forming an extreme ultraviolet (EUV) active photoresist film containing a tin alkene oxide moiety on a substrate disposed in a process chamber by 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, and patterning the EUV active photoresist film by exposing the substrate to EUV radiation.

[0006] According to an embodiment of the invention, there is provided a method of processing a substrate, the method including forming an extreme ultraviolet (EUV) active photoresist film comprising tin alkoxide, tin aryloxide, or tin carboxylate moieties on a substrate disposed in a process chamber by 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, aryloxide ligand, or tin carboxylate, and patterning the EUV active photoresist film by exposing the substrate to EUV radiation.

[0007] According to an embodiment of the invention, a method of forming an extreme ultraviolet (EUV) active photoresist film on a substrate includes 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 is performed during or after forming the EUV-active photoresist film.

[0008] For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which: [Brief description of the drawings]

[0009] [Figure 1A]1A-1D show cross-sectional views of an example substrate during a manufacturing process of forming an organometallic film on a substrate followed by EUV lithographic patterning according to various embodiments, showing an incoming substrate. [Figure 1B] 1A-1D show cross-sectional views of an example substrate during a manufacturing process of forming a metal-organic film on a substrate followed by EUV lithographic patterning in accordance with various embodiments, the substrate being shown after deposition of the metal-organic film on the substrate. [Figure 1C] 1A-1D show cross-sectional views of an example substrate during a manufacturing process of forming an organometallic film on a substrate followed by EUV lithographic patterning in accordance with various embodiments, showing the substrate after EUV exposure. [Figure 1D] 1A-1D illustrate cross-sectional views of an example substrate during a manufacturing process of forming an organometallic film on a substrate followed by EUV lithographic patterning, according to various embodiments, and show the substrate after a development step. [Diagram 2] 1 illustrates example reactions of metal-containing precursors and oxygen-containing precursors to form organometallic films, according to various embodiments. [Diagram 3] 1 illustrates an example processing system for depositing metal-organic films on a substrate, according to various embodiments, and illustrates a processing system for a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process, according to one embodiment. [Figure 4] 1 illustrates an example processing system for depositing metal-organic films on a substrate, according to various embodiments, and a plasma processing system for plasma enhanced chemical vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD) processes, according to another embodiment. [Diagram 5] 1 illustrates an example processing system for depositing metal-organic films on a substrate according to various embodiments, and further illustrates a liquid-based spin-on deposition system according to another embodiment. [Figure 6A] 1 shows a process flow diagram of a method of forming an organometallic film on a substrate according to various embodiments, illustrating the process flow of some embodiments. [Figure 6B]1 illustrates a process flow diagram for a method of forming an organometallic film on a substrate according to various embodiments, and illustrates a process flow for an alternative embodiment. [Figure 6C] 1 shows a process flow diagram for a method of forming an organometallic film on a substrate according to various embodiments, and illustrates a process flow for yet another embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Extreme ultraviolet (EUV) lithography can extend current photolithographic techniques beyond their optical limits by using smaller wavelengths of the imaging source to pattern features with small critical dimensions. EUV sources with wavelengths of about 13.5 nm can be used in state-of-the-art lithography tools, also called scanners. EUV radiation is strongly absorbed in a wide range of solid materials and gases, and therefore the radiation path must operate in a vacuum to avoid absorption by atmospheric gases such as H2O and O2.

[0011] EUV lithography typically utilizes an organic hardmask (e.g., a plasma enhanced chemical vapor deposition (PECVD) amorphous hydrogenated carbon ashable hardmask) patterned using conventional photoresist processes. During photoresist exposure, EUV radiation is absorbed in the resist and the underlying substrate to generate a cascade of high energy photoelectrons (~100 eV) and also low energy secondary electrons (~10 eV) that diffuse laterally a few nanometers. These electrons increase the extent of chemical reactions in the resist increasing its EUV dose sensitivity. However, a pattern of secondary electrons, which is random in nature, is superimposed on the optical image. This undesirable secondary electron exposure results in reduced resolution of the patterned resist, observable line edge roughness (LER), and line width variations. These defects are reproduced in the patterned material during the subsequent pattern transfer etch.

[0012] Metal oxide materials (including, for example, tin (Sn) bare metal) have proven particularly suitable for direct EUV photopatterning due to their strong absorption of EUV radiation. Unlike insulators such as traditional polymer-based chemically amplified resists (CARs), metal oxide materials are less susceptible to the effects of secondary electron exposure, because the secondary electrons can rapidly lose energy by scattering with the conduction electrons and thermalize.

[0013] The embodiments of the present disclosure describe a method for depositing a metalorganic film including tin (Sn) bare metal, which includes a metal oxide network and can be used as a photoresist for EUV patterning in the fabrication of integrated circuits. The metalorganic film can further include additional chemical elements such as halogens. According to one embodiment, the EUV-sensitive metalorganic film can be evaporated onto a semiconductor substrate. According to another embodiment, the EUV-sensitive metalorganic film can be deposited onto a semiconductor substrate using liquid exposure. The metalorganic film is then patterned by EUV exposure under vacuum conditions, followed by development of the pattern and removal of exposed or unexposed portions of the metalorganic film by dry or wet etching processes to form a metalorganic mask on the substrate. The formed metalorganic mask can then be used to pattern an underlying layer on the substrate by pattern transfer etching.

[0014] The methods described in this disclosure may advantageously enable metal-containing EUV-sensitive photoresists that have high EUV absorptivity and therefore better resist sensitivity compared to conventional CARs. Higher EUV absorptivity may allow for a reduction in the thickness of the photoresist required for acceptable performance. The metal-containing EUV-sensitive photoresists described in this disclosure may also advantageously exhibit better etch resistance after exposure than conventional CARs and a more uniform or homogenous chemical composition than CARs, both of which may be beneficial in mitigating smearing or line edge roughness issues.

[0015] An example manufacturing process step is described below with first reference to Figures 1A-1D, including forming, patterning, and developing an organometallic film as an EUV-sensitive photoresist film. Next, an example reaction for forming the organometallic film is shown in Figure 2. Then, Figures 3-5 show an example processing system for forming and depositing the organometallic film on a substrate. An example process flow diagram is described with reference to Figures 6A-6C, according to various embodiments. All figures are for illustrative purposes only and are not to scale.

[0016] 1A-1D illustrate cross-sectional views of an example substrate 100 during a manufacturing process involving forming a metal-organic film on the substrate followed by EUV lithographic patterning, according to various embodiments.

[0017] 1A shows 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 or include a semiconductor device, and may have undergone several processing steps, for example following conventional processing. Thus, the substrate 100 may include layers of semiconductors useful in various microelectronics. For example, a semiconductor structure may include the 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 some embodiments, the substrate 100 may include silicon germanium, silicon carbide, gallium arsenide, gallium nitride, or other compound semiconductors. In other embodiments, the substrate 100 includes heterogeneous layers, such as silicon germanium-on-silicon, gallium nitride-on-silicon, silicon carbon-on-silicon, as well as layers of silicon-on-silicon or SOI substrates. In various embodiments, the substrate 100 is patterned or embedded with other components of a semiconductor device.

[0019] FIG. 1B illustrates a cross-sectional view of substrate 100 after depositing organometallic film 102 onto substrate 100. FIG.

[0020] As shown in FIG. 1B, the metal-organic film 102 may be formed on the surface of the substrate 100 in one example. In various embodiments, although not shown, the substrate 100 may further include various layers useful for semiconductor device fabrication, which may be collectively considered as part of the substrate 100 in this disclosure. For example, in an embodiment, there may be a dielectric layer on the substrate 100 including a silicon-based dielectric material having a low dielectric constant (i.e., low k value), such as organosilicate glass (SiCOH), dense SiCOH, porous SiCOH, and other porous dielectric materials. In addition, there may be a hard mask layer on the substrate 100, which may be patterned in a subsequent etching process after EUV photopatterning. In various embodiments, the hard mask may include titanium nitride, titanium, titanium oxide, tantalum, tungsten carbide, other tungsten-based compounds, ruthenium-based compounds, or aluminum-based compounds. The hard mask may also be a carbon-based or silicon-based mask material. In addition, the metal-organic film 102 may be formed as part of a three-layer stack, which is typically used for photolithographic patterning. The tri-layer stack may be used to generate and transfer a pattern to a hard mask and then to an underlying layer, such as a dielectric layer of the substrate 100. In various embodiments, the tri-layer stack may include a bottom layer, an intermediate layer, and an organometallic film 102 as an EUV-sensitive photoresist. In one or more embodiments, the bottom layer may include a carbon material and may be formed by a spin-on process or deposition, such as CVD. The intermediate layer may include a silicon-based material, including, but not limited to, spin-on glass (SOG), silicon carbide, silicon oxide, silicon oxycarbide, silicon oxynitride, silicon nitride, tin oxide, and bottom anti-reflective coating (BARC). The intermediate layer 230 may also be formed by a spin-on process or deposition, such as CVD. For illustrative purposes, FIGS. 1A-1D only show the organometallic film 102 deposited directly on the substrate 100, but as discussed above, any suitable multi-layer structure may be present as part of the substrate 100 in various embodiments.

[0021] In various embodiments, the metalorganic film 102 may include tin (Sn). In an embodiment, the metalorganic film 102 may be a metal oxide network containing metal alkoxide, metal alkene oxide, metal aryloxide, or metal carboxylate groups. These groups bonded to the metal are generally represented by the formulas -OR, -OR', -OAr, and -OOCR, respectively, where R is an alkyl group, R' is an alkene group, and Ar is an aryl group. In various embodiments, the metalorganic film 102 is a polymeric film and may not have a highly regular structure, such as crystalline. The number of the above functional groups bonded to the metal atom may vary from one metal atom to another and range between 1 and 4. The deposition of the metalorganic film 102 may be performed by a dry process or a wet process. In various embodiments, the metalorganic film 102 may be deposited by vapor deposition, such as chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD), or plasma enhanced ALD (PEALD).

[0022] In an embodiment, the deposition process for the organometallic film 102 may include exposing the substrate 100 to two precursors, a tin-containing precursor and an oxygen-containing precursor, in a process chamber. The exposure to these 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 adsorbed 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 an embodiment, the exposure steps may be separated in time or space. Separating the exposure steps in time may be achieved by changing the gas composition in the process chamber. On the other hand, separating the exposure steps in space may be made possible by utilizing multiple spatially separated zones in the process chamber and transporting the substrate from one zone to another. To provide even better temporal separation of the exposure steps, deposition may further include evacuation, purging, or both evacuation and purging between the exposure steps. These additional steps may be beneficial in ensuring that reactions occur only on the surface and not in the gas phase. The ALD or pseudo-ALD method according to the present embodiment may be particularly advantageous in enabling layer-by-layer growth of organometallic films 102 with high uniformity.

[0023] In another embodiment, rather than an ALD-type process, the precursors may be fed simultaneously into the process chamber to grow the metalorganic film 102. Such an embodiment may be advantageous by allowing for sequential growth of the metalorganic film 102 in a single step. In this embodiment, the reaction between the precursors may or may not occur in the gas phase as well as on the surface.

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

[0025] In various embodiments, after the organometallic film 102 is formed on the substrate 100, an optional post-apply bake 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 substrate 100 after EUV exposure.

[0027] The method further includes exposing the substrate 100 to an EUV light pattern 104, as shown diagrammatically in FIG. 1C. A photomask may be used to generate the EUV light pattern 104. In response to the exposure to the EUV light pattern 104, a photochemical reaction may occur in the exposed regions 105 of the metalorganic film 102, while the unexposed regions 107 remain unchanged. As a result of the photochemical reaction, the exposed regions 105 may include a crosslinked metalorganic film, which may have substantially different material properties than the unreacted portions of the metalorganic film 102 (i.e., the unexposed regions 107). Such differences in material properties include, among others, volatility, reactivity, and / or solubility, which result from the tonality of the photoresist.

[0028] In one or more embodiments, as described further below, the organometallic film 102 may also include a photoacid generator (PAG) that releases a photoacid in response to EUV exposure. The generated photoacid may induce further chemical reactions within the organometallic film 102, which may improve tonality.

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

[0030] In FIG. 1D, the exposed regions 105 are developed and removed by a dry or wet etching process to form a patterned metalorganic mask including unexposed regions 107 and openings 108 that expose the underlying substrate 100. Conventionally, photoresist may be removed in a wet process by treating the substrate with a developer to dissolve the reacted (in the case of a positive resist) or unreacted (in the case of a negative resist) areas of the photoresist. A similar wet process may be applied to develop the metalorganic film 102 in various embodiments. Alternatively, a dry process may be used in other embodiments. The dry process may include, for example, a selective plasma etching process or a thermal process, advantageously eliminating the use of a developer solution. In some embodiments, the dry process may be performed using a reactive ion etching (RIE) process or an atomic layer etching (ALE). The openings 108 may then be used in an etching process to etch features in the substrate 100. In some embodiments, dry processes for forming and developing the organometallic film 102 may allow better process control on the nanoscale than wet processes, for example, to form features with critical dimensions of a few nanometers or sub-nanometers.

[0031] In various embodiments, after EUV exposure (FIG. 1C) and before the development step (FIG. 1D), an optional post-exposure bake (PEB) may be performed to further differentiate material properties between exposed and unexposed regions 105 and 107. In an embodiment, the PEB may be performed by heating the substrate 100 in a process chamber under vacuum or gas flow at a temperature between 70° C. and 250° C., such as in one embodiment at a temperature between 180° C. and 225° C.

[0032] 1A-1D, the organometallic film 102 is a negative photoresist. In other embodiments, the organometallic film 102 may form a positive photoresist, where the exposed regions 105 may be removed by a development step, leaving unexposed regions 107. In one embodiment, a positive photoresist may be enabled by performing an additional chemical treatment, such as polymerization, to increase the etch resistance of the unexposed regions 107 after EUV exposure, while a photochemical reaction in the exposed regions 105 reduces the etch resistance.

[0033] FIG. 2 illustrates an example reaction of a metal-containing precursor and an oxygen-containing precursor to form an organometallic film, according to various embodiments.

[0034] The metal-containing precursor may include an organotin compound that includes a ligand represented by the general formula SnL4 as shown in FIG. 2. In various embodiments, these ligands may include alkyl, amine, carboxylate, or halogen. In some embodiments, some ligands may include alkoxy groups. In one embodiment, all four ligands may be the same, but in another embodiment, they may be different. Exemplary tin-containing precursors include 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 include four halogen ligands, such as SnCl4 or SnI4. In various embodiments, a metal-containing precursor can be condensed with a co-reactant (eg, an oxygen-containing precursor) to form the organometallic film 102 .

[0035] As described in the previous embodiment, the oxygen-containing precursor may be used as a co-reactant in the formation of the organometallic film. In various embodiments, the oxygen-containing precursor may include a molecule having two or more reactive groups (e.g., diols), which may advantageously allow crosslinking of two or more molecules of the metal-containing precursor to form a stable polymer structure on the substrate. In some embodiments, the selection of bulky reactive groups may advantageously provide steric hindrance to each other, preventing excessive condensation prior to the EUV lithography process.

[0036] According to one embodiment, the oxygen-containing precursor may include an alkenol, and the deposited organometallic film may include a tin alkene oxide. An alkenol is a type of reactive structure or intermediate in organic chemistry, represented as an alkene (olefin), with at least one hydroxyl group attached to one end of an alkene double bond. By using an alkenol as the oxygen-containing precursor, a polymerizable structure may be advantageously incorporated into the formed organometallic film, which may be beneficial for enhancing the etch selectivity and thus the tonality as an EUV-sensitive photoresist.

[0037] According to another embodiment, the oxygen-containing precursor may include 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 include a tin alkoxide. Alkenediols may be used, which may include, but are 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-diene-1,2-diol, or (2Z,4E)-hepta-2,4-diene-2,6-diol.

[0038] According to yet another embodiment, the oxygen-containing precursor may include a phenolic compound and the deposited organometallic film includes a tin aryloxide film. As shown in Figure 2, an example of a phenolic compound includes catechol. The two hydroxyl groups of catechol may advantageously react with two different molecules of the tin-containing precursor such that each catechol unit crosslinks with a unit of tin oxide.

[0039] According to one embodiment, the oxygen-containing precursor may include a carboxylic acid and the deposited organometallic film may include a tin carboxylate. In some examples, the oxygen-containing precursor may include an alkene moiety and either (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 metalorganic film, where the additional polymerizable species reacts to form a polymer in the metalorganic film. The degree of polymerization in the metalorganic film during or after EUV exposure can be used to tailor the subsequent etch properties of the metalorganic film. Such modifications to the metalorganic film through additional polymerization and the resulting change in etch properties can advantageously improve the tonality of the metalorganic film as an EUV-sensitive photoresist. For example, in the case of a negative resist, the exposed areas of the metalorganic film should have a higher etch resistance than the unexposed areas, and additional polymerization can further increase the etch resistance of the exposed areas.

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

[0042] Additionally, in some embodiments, more than one metal-containing precursor and more than one oxygen-containing precursor may be utilized to form the organometallic film 102. The use of more than one metal-containing precursor and / or oxygen-containing precursor may advantageously allow for fine tuning of the overall physical and chemical properties (e.g., bulkiness, carbon-to-oxygen ratio, and / or hydrophobicity / hydrophilicity) of the resulting EUV-sensitive photoresist film of the organometallic film 102.

[0043] According to one embodiment, the method further includes incorporating a photoacid generator (PAG) into the organometallic film prior to EUV exposure. Incorporating a PAG into the photoresist generally results in enhanced sensitivity through chemical amplification. The PAG can release many photoacid molecules per absorbed photon, which diffuse and react with protecting groups in the photoresist backbone.

[0044] In one embodiment, the substrate is first exposed to an aluminum (Al) precursor having the general formula AlL3, and then exposed to a fluorinated alcohol (e.g., CF3OH) precursor to form an aluminum fluoroalkoxide moiety (e.g., Al(OCF3) xIncorporation of a PAG can be achieved by incorporating a PAG such as a fluorosiloxane (e.g., fluorosiloxane) into the metalorganic film as a PAG. The metalorganic film is then exposed to EUV radiation which generates photoacid from the aluminum fluoroalkoxide moieties and forms crosslinks that polymerize the exposed portions of the film.

[0045] In another embodiment, the substrate is first exposed to a boron (B) precursor represented by the general chemical formula BL3, and then exposed to a fluorinated alcohol precursor (e.g., CF3OH, etc.) or a fluorinated phenol precursor (e.g., C6F5OH, etc.) to form a boron fluoroalkoxide (e.g., B(OCF3) x etc.) or boron fluorophenoxide (e.g., B(OC6F5) x Incorporation of a PAG can be achieved by incorporating a boron fluoroalkoxide or boron fluorophenoxide moiety as a PAG into the organometallic film. The organometallic film is then exposed to EUV radiation which generates a photoacid from the boron fluoroalkoxide or boron fluorophenoxide moieties and forms crosslinks that polymerize the exposed portions of the film.

[0046] FIG. 3 illustrates a processing system for depositing metal-organic films on a substrate according to one embodiment.

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

[0048] In addition, the processing system 1 includes a substrate temperature control system 60 coupled to the substrate holder 20 and configured to raise and control the temperature of the 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, upon heating, transfers heat from the heat exchanger system. In addition, the temperature control element may include a heating / cooling element, such as a resistive heating element or a thermoelectric heater / cooler, that may be included in the substrate holder 20, as well as the chamber walls of the process chamber 10 and any other components within the processing system 1. The substrate temperature control system 60 may be configured to raise and control the substrate temperature, for example, from room temperature to about 350° C. to about 550° C. Alternatively, the substrate temperature may range, for example, from about 150° C. to about 350° C. It should be understood, however, that the substrate temperature is selected based on a desired temperature to produce the deposition of a particular organometallic film on the surface of a given substrate.

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

[0050] 3, a single processing element (10, 20, 30, 40, 42, 44, 46, 48, 50, and 60) is shown, but this is merely an example, and the processing system 1 may include any number of processing elements with any number of controllers associated with the processing elements, in addition to independent processing elements. The controller 70 may be used to configure any number of processing 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 processing elements. The controller 70 may include a number of applications for controlling one or more of the processing elements. For example, the controller 70 may include a graphic user interface (GUI) component (not shown) that may provide an easy-to-use interface that allows a user to monitor and / or control one or more processing elements.

[0051] Still referring to FIG. 3, the processing system 1 may be configured to process 200 mm substrates, 300 mm substrates, 450 mm substrates, or larger sized substrates. Indeed, as will be appreciated by those skilled in the art, it is contemplated that the processing system 1 may be configured to process substrates, wafers, or LCDs regardless of their size. Accordingly, the embodiments of the present disclosure are described primarily in the context of processing semiconductor substrates, but are not limited thereto. Alternatively, a batch processing system capable of processing multiple substrates simultaneously may be utilized to deposit the organometallic films described in the embodiments of the present invention.

[0052] In some embodiments, several methods can be utilized to introduce the tin-containing precursor gas and the oxygen-containing precursor gas into the process chamber 10. One method includes vaporizing the precursors using separate bubblers or direct liquid injection (DLI) systems, or a combination of these, and then mixing in the gas phase before introduction in or into the process chamber 10. DLI systems have been shown to reduce premature thermal decomposition of the precursors over bubbling methods. By separately controlling the vaporization rate of each precursor, a desired stoichiometric composition can be achieved in the deposited film. Another method of delivering the first and second precursors includes separately controlling two or more different liquid sources (neat precursors or precursor solutions), which are then mixed before entering a common vaporizer. This method can be utilized when the precursors are compatible in solution or liquid form and have similar vaporization properties. Yet another method of delivering the first and second precursors includes controlling the flow of the liquid precursor mixture (neat precursors or precursor solutions) into a common vaporizer. Other methods include using compatible mixed solid or liquid precursors in a bubbler. The liquid source precursor may include neat liquid precursors or solid or liquid precursors dissolved in a compatible solvent. Potential compatible solvents include, but are not limited to, ionic liquids, hydrocarbons (aliphatic, olefinic, and aromatic), amines, esters, glymes, crown ethers, ethers, and polyethers. In some cases, it may be possible to dissolve one or more compatible solid precursors in one or more compatible liquid precursors. It will be apparent to one skilled in the art that by controlling the relative concentration levels of the first and second precursors in the gas pulse, it is possible to deposit a film with a desired stoichiometric composition.

[0053] 3, the purge gas supply system 44 is configured to introduce a purge gas into the process chamber 10. For example, introduction of the purge gas may occur between introduction of pulses of the tin-containing precursor and oxygen-containing precursor gases into the process chamber 10. The purge gas may include an inert gas, such as 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 clamping system or an electrical clamping system, such as an electrostatic clamping system, for securing the substrate 22 to the top surface of the substrate holder 20. Additionally, the substrate holder 20 may further include a substrate backside gas delivery system configured to introduce gas to the backside of the substrate 22 to improve the gas gap thermal conductance between the substrate 22 and the substrate holder 20. Such a system may be utilized when temperature control of the substrate is required as the temperature increases or decreases. For example, the substrate backside gas system may include a two-zone gas distribution system and may independently vary the helium gas cap pressure between the center and edge of the substrate 22.

[0055] As further shown in FIG. 3, the process chamber 10 is further coupled via duct 38 to a pressure control system 32 including a vacuum pumping system 34 and a valve 36 configured to controllably evacuate the process chamber 10 to a pressure suitable for forming an organometallic film on the substrate 22 and for use with tin-containing precursor and oxygen-containing precursor gases. The vacuum pumping system 34 may include a turbomolecular vacuum pump (TMP) or cryopump capable of pumping speeds of up to about 5000 liters per second (and greater), 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 may be configured to control the process chamber pressure between about 0.1 Torr and about 100 Torr, for example, during deposition of the organometallic film.

[0056] The precursor delivery systems 40 and 42, the purge gas delivery system 44, the auxiliary gas delivery systems 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 actuated valves, electromechanical (solenoid) valves, and / or fast pulse gas injection valves. The gases may be pulsed into the process chamber 10 in a sequential and alternating manner, with each gas pulse having a length of, for example, between about 0.1 seconds and about 100 seconds. Alternatively, each gas pulse may have a length of, for example, between about 1 second and about 10 seconds. An exemplary gas pulse length for the precursor gases may be between 0.3 seconds and 3 seconds, for example, 1 second. An exemplary gas pulse length for the tin-containing precursor and oxygen-containing precursor gases may be between 0.3 seconds and 3 seconds, for example, 1 second. An exemplary purge gas pulse may be between 1 second and 20 seconds, for example, 3 seconds.

[0057] 3, the controller 70 may include a microprocessor, memory, and digital I / O ports capable of generating sufficient control voltages to communicate and activate inputs to the processing system 1 and monitor outputs from the processing system 1. Additionally, the controller 70 may be coupled to and exchange information with the process chamber 10, the substrate holder 20, the upper assembly 30, the precursor delivery systems 40 and 42, the purge gas delivery system 44, the auxiliary gas delivery systems 46, 48, and 50, the substrate temperature control system 60, and the pressure control system 32. For example, to perform a deposition process, the controller 70 may utilize a program stored in the memory to activate inputs to the aforementioned components of the processing system 1 according to a process recipe.

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

[0059] FIG. 4 illustrates a plasma processing system 2 that may be configured to perform a PEALD or PECVD process in addition to being capable of performing an ALD or CVD process. The plasma processing system 2 is similar to the processing system 1 described in FIG. 3, but further includes a plasma generation system configured to generate a plasma during at least a portion of the gas exposure in 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 a 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 the RF power is coupled to the plasma in the process chamber 10. The electrode may be formed on the upper assembly 31 and may be configured to face the substrate holder 20. The impedance matching network may be configured to optimize the transfer of RF power from the RF generator to the plasma by matching an output impedance of the matching network to an input impedance of the process chamber including the electrode and the plasma. For example, the impedance matching network helps to improve the transfer of RF power to the plasma in the process chamber 10 by reducing reflected power. Match network topologies (eg, L-type, π-type, T-type, etc.) and automatic control schemes 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 through which RF power is coupled to the plasma in the process chamber 10. The antenna may include, for example, a helical coil or a solenoid coil, such as in an inductively coupled plasma source or a helicon source, or the antenna may include 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 through which microwave power is coupled to the plasma in the process chamber 10. The coupling of microwave power may be accomplished using electron cyclotron resonance (ECR) techniques or may be employed using surface wave plasma techniques.

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

[0063] In addition, the plasma processing system 2 includes a remote plasma system 56 for remotely providing a plasma excitation gas prior to flowing the plasma excitation gas into the process chamber 10 where the plasma excitation gas is exposed to the substrate 22. The remote plasma system 56 may include, for example, a microwave frequency generator. The pressure of the process chamber may be from about 0.1 Torr to about 10 Torr, or from about 0.2 Torr to about 3 Torr.

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

[0065] FIG. 5 shows a schematic of a processing system 3 for processing a substrate according to yet another embodiment. The processing system 3 can be a semi-closed spin-on deposition system, similar to those currently employed by the semiconductor industry to coat substrates (wafers) with a photoresist layer. The semi-closed configuration allows for fume control and minimizes exhaust emissions. The processing system 3 includes a process chamber 310 including a substrate holder 312 for supporting, heating, and rotating (spinning) the substrate 302, a rotating means 318 (e.g., a motor), and a liquid delivery nozzle 314 configured to provide a processing liquid 316 to an upper surface of the substrate 302. The liquid supply systems 304, 306, and 308 supply different processing liquids to the liquid delivery nozzle 314. The different processing liquids can include, for example, a first reactant (e.g., a tin-containing precursor) in a first liquid, a second reactant (e.g., an oxygen-containing precursor) in a second liquid, and a rinsing liquid. According to other embodiments, the processing system 300 may include additional liquid dispensing nozzles (not shown) for providing different liquids to the substrate. An exemplary rotation speed may be between about 500 rpm and about 1500 rpm, such as 1000 rpm, during exposure of the top surface of the substrate 302 to the processing liquid 316.

[0066] The processing system 3 further includes a controller 320 coupled to and capable of controlling the process chamber 310, liquid supply systems 304, 306, and 308, a liquid delivery nozzle 314, a rotating means 318, and a means for heating the substrate holder 312. The substrate 302 may be under an inert atmosphere during film deposition. The processing system 300 may be configured to process 200 mm substrates, 300 mm substrates, or substrates of larger sizes. As will be appreciated by those skilled in the art, the processing system 300 may be configured to process substrates, wafers, or LCDs regardless of their size. Thus, although aspects of the present invention are described in the context of processing semiconductor substrates, the present invention is not so limited.

[0067] The processing systems described above with reference to Figures 3-5 are merely examples and any other reasonable systems and configurations are possible. For example, the plasma processing system 2 of Figure 4 may include multiple spatially separated zones within the process chamber 10, and a deposition process may be performed by moving the substrate through the spatially separated zones using a rotatable stage.

[0068] 6A-6C show process flow diagrams of methods for forming an EUV active photoresist layer according to various embodiments. The process flow may be described using the figures described above (e.g., FIGS. 1A-1C), and therefore will not be described again in detail.

[0069] In FIG. 6A, the process flow 600 may begin with forming an EUV-sensitive photoresist film containing a tin alkene oxide on a substrate in 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). The oxygen-containing precursor may include an alkenol to enable the formation of a tin alkene oxide. In various embodiments, the precursor may be a gas or a liquid, and thus the exposing step described above may be a dry or wet process. In some embodiments, an optional intermediate step may be performed between the exposing steps to evacuate or purge the process chamber and / or to rinse the substrate (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 exposing step is repeated as part of a cyclic process, the various process conditions (e.g., precursor feed rate, temperature, pressure, processing time, etc.) for each step of each cycle may be the same in some embodiments, but may be different in other embodiments. In alternative embodiments, the exposure steps may overlap in time, either in whole or in part, allowing the process to be more continuous rather than stepwise. Once the EUV-sensitive photoresist film is formed on the substrate, EUV lithographic patterning may be performed by exposing the substrate to EUV radiation (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 in the EUV-sensitive photoresist film for enhanced tonality (block 625). After EUV exposure, subsequent steps such as a development step and a pattern transfer etch process may be performed.

[0070] In FIG. 6B, process flow 602 is essentially the same as process flow 600, except that the oxygen-containing precursor may have a different composition than the previous embodiment to enable EUV-sensitive photoresist films that include tin alkoxides, tin aryloxides, or tin carboxylates.

[0071] In FIG. 6C, the process flow 604 may begin by first exposing the substrate to a tin-containing precursor (block 610) and then exposing the substrate to an oxygen-containing precursor (block 620). Furthermore, after the EUV-sensitive photoresist film is formed, a step of incorporating a photoacid generator (PAG) may be performed (block 624). In various embodiments, the incorporation of the PAG may be achieved by exposing the substrate to a PAG precursor, such as a pair of an aluminum-containing precursor or a boron-containing precursor and a fluorinated alcohol precursor or a fluorinated phenol precursor. In some embodiments, this step of incorporating the PAG may be performed simultaneously while forming the EUV-sensitive photoresist film. Thus, exposing the substrate to the PAG precursor (block 624) may overlap in time, in whole or in part, with the other exposure steps (blocks 610 and 620).

[0072]

[0023] Illustrative embodiments of the present invention are summarized herein. Other embodiments can be seen throughout the specification and claims appended hereto.

[0073] Example 1. A method of treating a substrate, comprising forming an extreme ultraviolet (EUV) active photoresist film containing a tin alkene oxide moiety on a substrate disposed in a process chamber by 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, and patterning the EUV active photoresist film by exposing the substrate to EUV radiation.

[0074] Example 2. The method of example 1, wherein the tin-containing precursor and the oxygen-containing precursor are gaseous, and the method further comprises evacuating or purging the process chamber between the exposing steps.

[0075] Example 3. The method of any one of Examples 1 or 2, wherein the tin-containing precursor and the oxygen-containing precursor are liquids, and the method further comprises rinsing the substrate with a solvent between the exposing steps to remove excess amounts of the tin-containing precursor or the oxygen-containing precursor.

[0076] Example 4. The method of example 1, wherein the exposing steps overlap in time.

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

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

[0079] Example 7. The method of any one of Examples 1-6, 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. The method of any one of Examples 1-7, wherein the patterning comprises crosslinking the EUV active photoresist film by polymerizing an alkene moiety of a tin alkene oxide.

[0081] Example 9. The method of any one of Examples 1-8, wherein crosslinking occurs only in EUV exposed areas of the EUV active photoresist film during patterning of the EUV active photoresist film with EUV lithography.

[0082] Example 10. A method of treating a substrate, comprising forming an extreme ultraviolet (EUV) active photoresist film comprising tin alkoxide, tin aryloxide, or tin carboxylate moieties on a substrate disposed in a process chamber by 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, aryloxide ligand, or tin carboxylate, and patterning the EUV active photoresist film by exposing the substrate to EUV radiation.

[0083] Example 11. The method of example 10, wherein the oxygen-containing precursor comprises an alcohol.

[0084] Example 12. The method of any one of Examples 10 or 11, wherein the oxygen-containing precursor comprises a diol.

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

[0086] Example 14. The method of any one of Examples 10-13, wherein the EUV active photoresist film comprises a tin aryloxide and the oxygen-containing precursor comprises a phenolic compound.

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

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

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

[0090] Example 18. A method of 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 an EUV-active photoresist film comprising tin and oxygen, and incorporating a photoacid generator (PAG) into the EUV-active photoresist film, wherein the incorporation is performed during or after the formation of the EUV-active photoresist film.

[0091] Example 19. The method of example 18, wherein the incorporating comprises exposing the substrate to an aluminum (Al) precursor and exposing the substrate to a fluorinated alcohol precursor to incorporate an aluminum fluoroalkoxide moiety into the EUV-active photoresist film as a photoacid generator (PAG).

[0092] Example 20. The method of any one of Examples 18 or 19, wherein the incorporating 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 moiety into the EUV active photoresist film as a photoacid generator (PAG).

[0093] Example 21. 1. A method for processing a substrate, comprising: providing a substrate in a process chamber; and forming an EUV-sensitive film on the substrate by exposing the substrate to a tin (Sn)-containing precursor that forms an adsorbed layer on the substrate, and exposing the substrate to an oxygen-containing precursor that reacts with the adsorbed layer, the oxygen-containing precursor comprising: a) an alkenol that reacts with the adsorbed layer to form a tin alkene oxide film on the substrate; b) an alcohol that reacts with the adsorbed layer to form a tin alkoxide film on the substrate; c) an alcohol that reacts with the adsorbed layer to form a tin alkene oxide film on the substrate; d) a diol that reacts with the adsorbed layer to form a tin alkoxide film on the substrate; e) a phenol that reacts with the adsorbed layer to form a tin aryloxide film on the substrate; f) a carboxylic acid that reacts with the adsorbed layer to form a tin carboxylate film on the substrate; or g) an alkene moiety to form a tin carboxylate film on the substrate, and either a) at least one carboxylic acid group and at least one alcohol group, or b) two carboxylic acid groups.

[0094] Example 22. The method of example 21, wherein the tin-containing precursor and the oxygen-containing precursor are gaseous, and the method further comprises evacuating, purging, or both evacuating and purging the process chamber during the exposing step.

[0095] Example 23. The method of any one of Examples 21 or 22, wherein the tin-containing precursor and the oxygen-containing precursor are liquids, and the method further comprises rinsing the substrate between the exposing steps.

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

[0097] Example 25. The method of any one of Examples 21-24, further comprising exposing the substrate to an aluminum (Al) precursor and exposing the substrate to a fluorinated alcohol precursor to incorporate aluminum fluoroalkoxide moieties into the metal oxide film, and exposing the metal oxide film to EUV radiation that generates a photoacid from the aluminum fluoroalkoxide moieties and forms cross-links that polymerize the exposed portions of the metal oxide film.

[0098] Example 26. The method of any one of Examples 21-25, further comprising exposing the substrate to a boron (B) precursor and exposing the substrate to a fluorinated alcohol precursor or a fluorinated phenol precursor to incorporate boron fluoroalkoxide or boron fluorophenoxide moieties into the metal oxide film, and exposing the metal oxide film to EUV radiation that generates a photoacid from the boron fluoroalkoxide or boron fluorophenoxide moieties to form crosslinks that polymerize the exposed portions of the metal oxide film.

[0099] Example 27. The method of any one of Examples 21-26, 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. The method of any one of Examples 21-27, further comprising transferring the substrate to a lithography system for EUV exposure.

[0101] While the present invention has been described with reference to exemplary embodiments, this specification is not intended to be construed in a limiting sense. Various modifications and combinations of the exemplary embodiments, as well as other embodiments of the present invention, will become apparent to those skilled in the art upon reference to this specification. It is therefore intended that the appended claims cover any such modifications or embodiments.

Claims

1. 1. A method for processing a substrate, comprising: forming an extreme ultraviolet (EUV) active photoresist film containing a tin alkene oxide, a tin alkoxide, a tin aryl oxide, or a tin carboxylate moiety on the substrate disposed in a process chamber; 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 the tin alkene oxide, the tin alkoxide, the tin aryloxide, or the tin carboxylate, wherein the tin-containing precursor and the oxygen-containing precursor comprise liquids; said forming by patterning the EUV active photoresist film by exposing the substrate to EUV radiation; A method comprising:

2. The method of claim 1, wherein exposing the substrate to the tin-containing precursor and exposing the substrate to the oxygen-containing precursor are separated in time by varying the precursor composition within the process chamber, or in space by using multiple separated zones within the process chamber.

3. The method of claim 1, further comprising rinsing the substrate with a solvent between the exposing steps to remove excess amounts of the tin-containing precursor or the oxygen-containing precursor.

4. The method of claim 1 , wherein the exposing steps overlap in time.

5. The method of claim 1 , further comprising repeating the exposing step.

6. The method of claim 1 , wherein the oxygen-containing precursor comprises an alkenol.

7. The tin-containing precursor is trimethyltin chloride (Me ３ SnCl), dimethyltin dichloride (Me ２ SnCl ２ ), methyltin trichloride (MeSnCl ３ ), tris(dimethylamino)methyltin(IV) ((CH ３ ) ２ N) ３ SnMe), or (dimethylamino)trimethyltin(IV) ((CH ３ ) ２ N) SnMe ３ 2. The method of claim 1 , comprising:

8. 2. The method of claim 1, wherein said patterning comprises cross-linking the EUV active photoresist film by polymerizing alkene moieties of the tin alkene oxide.

9. 10. The method of claim 8, wherein said cross-linking occurs only in EUV exposed areas of said EUV active photoresist film during said patterning of said EUV active photoresist film with EUV lithography.

10. 1. A method for processing a substrate, comprising: forming an extreme ultraviolet (EUV) active photoresist film comprising a tin alkene oxide, a tin alkoxide, a tin aryl oxide, or a tin carboxylate moiety on the substrate disposed in a process chamber; 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 the tin alkene oxide, the tin alkoxide, the tin aryloxide, or the tin carboxylate, wherein exposing the substrate to the tin-containing precursor and exposing the substrate to the oxygen-containing precursor are separated in time by varying precursor composition in the process chamber or in space by using multiple separated zones in the process chamber; said forming by patterning the EUV active photoresist film by exposing the substrate to EUV radiation; A method comprising:

11. The method of claim 10 , wherein the oxygen-containing precursor comprises an alcohol.

12. The method of claim 10 , wherein the oxygen-containing precursor comprises a diol.

13. The method of claim 12 wherein the diol is ethylene glycol.

14. 11. The method of claim 10, wherein the EUV active photoresist film comprises the tin aryloxide and the oxygen-containing precursor comprises a phenolic compound.

15. 11. The method of claim 10, wherein the EUV active photoresist film comprises the tin carboxylate and the oxygen-containing precursor comprises a carboxylic acid.

16. 11. The method of claim 10, wherein the EUV active photoresist film comprises the tin carboxylate and the oxygen-containing precursor comprises an alkene moiety, a carboxyl group, and a hydroxyl group.

17. 11. The method of claim 10, wherein the EUV active photoresist film comprises the tin carboxylate and the oxygen-containing precursor comprises an alkene moiety and two carboxyl groups.

18. 1. A method for forming an extreme ultraviolet (EUV) active photoresist film on a substrate, 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; incorporating a photoacid generator (PAG) into the EUV active photoresist film, 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 aluminum fluoroalkoxide moieties, boron fluoroalkoxide moieties, or boron fluorophenoxide moieties as photoacid generators (PAGs) into the EUV active photoresist film, the incorporation being performed during or after formation of the EUV active photoresist film; By incorporating A method comprising:

19. The incorporation exposing the substrate to the aluminum (Al) precursor; exposing the substrate to the fluorinated alcohol precursor to incorporate the aluminum fluoroalkoxide moieties into the EUV active photoresist film as the photoacid generator (PAG); 20. The method of claim 18, comprising:

20. The incorporation exposing the substrate to the boron (B) precursor; exposing the substrate to the fluorinated alcohol precursor or the fluorinated phenol precursor to incorporate the boron fluoroalkoxide or the boron fluorophenoxide moiety into the EUV active photoresist film as the photoacid generator (PAG); 20. The method of claim 18, comprising:

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