Method for forming a moisture barrier on a photosensitive organometallic oxide

Abstract

Various embodiments of methods are provided for forming a moisture barrier layer on an EUV-active photoresist film and then patterning the EUV-active photoresist film with EUV lithography. According to one embodiment, the method disclosed herein can form an EUV-active photoresist film on a surface of a semiconductor substrate and a moisture barrier layer containing a hydrocarbon polymer on the EUV-active photoresist film, after which the EUV-active photoresist film is patterned with EUV lithography to form a patterned photoresist on the substrate surface. In some embodiments, a first hydrocarbon polymer layer can be formed on the substrate surface, after which an EUV-active photoresist film is formed on the first hydrocarbon polymer layer. By providing a hydrocarbon polymer layer above and / or below the EUV-active photoresist film, the disclosed method improves the performance of the EUV-active photoresist film by protecting the upper / lower surfaces of the EUV-active photoresist film from undergoing undesired chemical reactions.

Description

[Technical Field]

[0001] Cross-references to related patents and applications This application claims priority to U.S. Provisional Patent Application No. 63 / 404,772, filed September 8, 2022, entitled "Method of Forming a Moisture Barrier on Photosensitive Organometallic Oxides," the disclosure of which is expressly incorporated herein by reference in its entirety. This application is related to U.S. Patent Application No. 18 / 216,168, filed June 29, 2023, entitled "Method of Forming Photosensitive Organometallic Oxides by Chemical Vapor Polymerization," the disclosure of which is expressly incorporated herein by reference in its entirety.

[0002] The present invention relates generally to extreme ultraviolet (EUV) lithography, and in particular embodiments, to EUV-active films and methods of forming the same. [Background technology]

[0003] Generally, semiconductor devices, such as integrated circuits (ICs), are fabricated by sequentially depositing and patterning layers of dielectric, conducting, and semiconducting materials over a semiconductor substrate to form a network of electronic components and interconnect elements (e.g., transistors, resistors, capacitors, metal lines, contacts, and vias) integrated into a monolithic structure. Each successive technology node reduces costs by shrinking the minimum feature size and approximately doubling component packing density.

[0004] A common patterning method is to use a photolithography process to expose a coating of photoresist over a target layer to a pattern of actinic radiation and then transfer the relief pattern into the target layer or an underlying hard mask layer formed over the target layer. With this technique, the minimum feature size will be limited by the resolution of the optical system. Feature size scaling for advanced technology nodes is driving lithography to improve resolution. For technology nodes below 10 nm (e.g., 7 nm and 5 nm technology nodes), 13.5 nm extreme ultraviolet (EUV) lithography is commonly used to pattern photoresistive films with EUV radiation.

[0005] EUV lithography technology offers significant advantages in patterning sub-10 nm features with its high optical resolution. However, one major engineering challenge for EUV lithography is that photoresists developed for conventional photolithography systems may not meet the cost and / or quality requirements for patterning sub-10 nm features. For example, chemically amplified resists (CARs) or similar polymer resists commonly used in 193 nm lithography are typically fabricated using liquid-based spin-on techniques that consume significant amounts of complex metal cluster precursors, resulting in prohibitive costs. CARs also tend to have low absorption coefficients at 13.5 nm and therefore may suffer from poor sensitivity. Furthermore, diffusion of photoactive species in CARs can cause blurring in subsequently formed patterns and increase line edge roughness (LER).

[0006] As an alternative to CAR, vapor-deposited metal oxide-containing films have been investigated for use as EUV-active hard masks in EUV lithography techniques. For example, U.S. Patent No. 9,996,004, entitled "EUV Photopatterning of Vapor-Deposited Metal Oxide-Containing Hardmasks," describes various processes for forming metal oxide-containing hard masks utilized in EUV patterning. In the '004 patent, EUV-sensitive metal oxide-containing films are deposited on semiconductor substrates by chemical vapor deposition (CVD) or atomic layer deposition (ALD). During the deposition process, organotin oxide precursors are reacted with a carbon dioxide-containing plasma at relatively high deposition temperatures (e.g., 250°C to 350°C) to deposit an EUV-sensitive metal oxide-containing film on the semiconductor substrate. After CVD / ALD deposition, the metal oxide-containing film (e.g., metal oxide resist (MOR) film) is transferred to an EUV patterning tool and patterned by direct EUV exposure (i.e., without the use of a photoresist), followed by pattern development, to form a metal oxide-containing hard mask.

[0007] The process described in the '004 patent suffers from various drawbacks. For example, the deposition process described in the '004 patent involves reacting various organotin oxide precursors with an oxidizing agent (e.g., carbon dioxide or carbon monoxide) in a typical CVD / ALD process to form a solid metal oxide-containing film on a semiconductor substrate. The oxidizing agent utilized in the CVD / ALD deposition process creates weak and unstable bonds (e.g., Sn—OH and Sn—O—Sn bonds) that increase the density of the metal oxide-containing film and worsen the EUV light sensitivity of the subsequently formed hard mask. Summary of the Invention [Problem to be solved by the invention]

[0008] Innovations in EUV photolithography technology are needed to meet the cost and quality requirements for patterning in the sub-10 nm node region, and to meet these needs, it may be desirable to develop a new class of photoresists for EUV lithography with better performance. [Means for solving the problem]

[0009] The present disclosure relates generally to photolithography processes, and more specifically to improved process flows and methods for protecting EUV-active photoresist films formed over semiconductor substrates.

[0010] The improved process flows and methods described herein protect EUV-active photoresist films by providing a hydrocarbon polymer layer above and / or below the EUV-active photoresist film. The hydrocarbon polymer layer formed above the EUV-active photoresist film functions as a barrier layer that prevents undesired reactions on the top surface of the EUV-active photoresist film. In one non-limiting example, the hydrocarbon polymer layer formed above the EUV-active photoresist film can function as a moisture control / barrier layer that prevents the EUV-active photoresist film from chemically reacting with moisture in the ambient environment and forming undesired metal oxide-metal species on the surface of the photoresist. The hydrocarbon polymer layer formed below the EUV-active photoresist film prevents the EUV-active photoresist film from chemically reacting with the underlying silicon-containing substrate and forming undesired metal oxide-silicon species on the substrate surface. Therefore, the hydrocarbon polymer layer described herein improves the performance of EUV-active photoresist films by preventing undesired reactions on the top and bottom surfaces of the photoresist.

[0011] According to one embodiment, a method for processing a semiconductor substrate is provided herein. The method may generally include forming an extreme ultraviolet (EUV)-active photoresist film on a surface of the semiconductor substrate, where the EUV-active photoresist film comprises an organometallic oxide; plasma-depositing a moisture barrier layer containing a hydrocarbon polymer on the EUV-active photoresist film; and patterning the EUV-active photoresist film with EUV lithography to form a patterned photoresist on the surface of the semiconductor substrate.

[0012] According to another embodiment, a method for processing a semiconductor substrate is provided herein. The method may generally include plasma depositing a first hydrocarbon polymer layer on a surface of the semiconductor substrate; plasma depositing an extreme ultraviolet (EUV)-active photoresist film on the first hydrocarbon polymer layer; plasma depositing a second hydrocarbon polymer layer on the EUV-active photoresist film; and patterning the EUV-active photoresist film with EUV lithography to form a patterned photoresist on the surface of the semiconductor substrate.

[0013] In various embodiments, the EUV-active photoresist film disclosed herein can be an organometallic oxide or metal oxide resist (MOR). For example, the EUV-active photoresist film can be an organometallic oxide containing tin (Sn), zirconium (Zr), indium (In), antimony (Sb), bismuth (Bi), zinc (Zn), hafnium (Hf), aluminum (Al), or a combination thereof. In some embodiments, the EUV-active photoresist film can be an organometallic oxide having polymerized carbon-carbon bonds.

[0014] The first hydrocarbon polymer layer and / or the second hydrocarbon polymer layer (i.e., moisture barrier layer) can contain a wide variety of hydrocarbon polymers. In some embodiments, the hydrocarbon polymer can include carbon and hydrogen. For example, the hydrocarbon polymer can include a) carbon, hydrogen, and oxygen; b) carbon, hydrogen, oxygen, and nitrogen; or c) carbon, hydrogen, and nitrogen.

[0015] The first hydrocarbon polymer layer and / or the second hydrocarbon polymer layer (i.e., moisture barrier layer) can be formed by plasma excitation of a wide variety of precursors. For example, hydrocarbon precursors, aldehyde precursors, and / or amine precursors can be plasma excited to form one or more of the first and second hydrocarbon polymer layers. In some embodiments, the plasma excitation can further include an additional gas, such as, for example, hydrogen (H), helium (He), argon (Ar), neon (Ne), xenon (Xe), nitrogen (N), carbon monoxide (CO), ammonia (NH), or hydrogen sulfide (HS).

[0016] In some embodiments, a hydrocarbon precursor may be used to form the hydrocarbon polymer layer. The hydrocarbon precursor may be represented by the formula C α H β where α is an integer greater than or equal to 1 and β is an integer greater than or equal to 1. α H β Non-limiting examples of hydrocarbon precursors having the formula include, but are not limited to, a methyl group (CH), acetylene (C2H2), ethylene (C2H4), a propyl group (C3H7), and styrene (C6H5CH=CH2).

[0017] In other embodiments, an aldehyde precursor may be used to form the hydrocarbon polymer layer. The aldehyde precursor may be represented by the formula C α H β O γ (wherein α is an integer greater than or equal to 1, β is an integer greater than or equal to 1, and γ is an integer greater than or equal to 1). α H β O γAn example of an aldehyde precursor having the formula (I) is benzaldehyde (C6H5CHO).

[0018] In yet other embodiments, an amine precursor may be used to form the hydrocarbon polymer layer. The amine precursor may be represented by the formula C α H β N γ O δ (wherein α is an integer greater than or equal to 1, β is an integer greater than or equal to 1, γ is an integer greater than or equal to 1, and δ is an integer greater than or equal to 0). α H β N γ O δ An example of an amine precursor having the formula (I) is phenylenediamine (C6H4(NH2)2).

[0019] A wide variety of plasma processing chambers can be utilized to plasma deposit the first and / or second hydrocarbon polymer layers (i.e., moisture barrier layers). For example, a plasma processing system having a remote plasma source, such as a capacitively coupled plasma (CCP) processing chamber, an inductively coupled plasma (ICP) processing chamber, or a radio frequency (RF), very high frequency (VHF), or microwave frequency (MWF) source, can be used. In one embodiment, the plasma deposition step used to plasma deposit the first and / or second hydrocarbon polymer layers (i.e., moisture barrier layers) can be performed in a CCP processing chamber having a source frequency of 13.56 MHz to 60 MHz, a source power of about 10 W to about 500 W, an ion energy of about 50 eV or less, a gas pressure of about 100 mTorr to about 20 Torr, and a substrate temperature of less than about 100°C.

[0020] In some embodiments, a relatively thin (e.g., about 1 nm to 10 nm) moisture barrier layer (or second hydrocarbon polymer layer) can be deposited on the EUV-active photoresist film. In some embodiments, the EUV-active photoresist film can be patterned by (a) exposing the moisture barrier layer and the EUV-active photoresist film to EUV radiation, whereby reacted areas of the EUV-active photoresist film exposed to EUV radiation are converted to reacted photoresist, while areas of the EUV-active photoresist not exposed to EUV radiation remain unreacted; (b) removing the moisture barrier layer; and (c) removing specific areas of the EUV-active photoresist to form a photoresist pattern.

[0021] In some embodiments, the patterning step may remove unreacted areas of the EUV-active photoresist to form a first photoresist pattern (e.g., a negative photoresist) on the substrate. In some embodiments, the method may further include selectively depositing a material film on top of the first photoresist pattern relative to the exposed surface of the semiconductor substrate.

[0022] In some embodiments, the patterning step may remove reacted areas of the EUV-active photoresist to form a second photoresist pattern (e.g., a positive photoresist) on the substrate. In some embodiments, the method may further include selectively depositing a material film on the exposed surface of the semiconductor substrate relative to the second photoresist pattern.

[0023] In other embodiments, a relatively thick (e.g., greater than about 10 nm) moisture barrier layer (or second hydrocarbon polymer layer) can be deposited on the EUV-active photoresist film. In such embodiments, the EUV-active photoresist film can be patterned by (a) exposing the moisture barrier layer to EUV radiation, where a first region of the moisture barrier layer exposed to EUV radiation is converted into a reacted moisture barrier layer, and a second region of the moisture barrier layer not exposed to EUV radiation remains unreacted; (b) removing the first region of the moisture barrier layer that has been converted into a reacted moisture barrier layer to form a patterned moisture barrier layer; and (c) exposing the EUV-active photoresist film to EUV radiation through the openings in the patterned moisture barrier layer, where the reacted region of the EUV-active photoresist film exposed to EUV radiation is converted into a reacted photoresist, and the unreacted region of the EUV-active photoresist not exposed to EUV radiation remains unreacted. In some embodiments, the method may further include selectively depositing a material film on top of the reacted photoresist and removing the patterned moisture barrier layer. The patterned moisture barrier layer may be removed before or after the material film is selectively deposited on top of the reacted photoresist.

[0024] Various embodiments of methods for processing semiconductor substrates, and more particularly, for forming a moisture barrier layer over an EUV-activated photoresist film, are provided herein. It should be understood that the order of discussion of the various steps as described herein is presented for clarity. In general, these steps can be performed in any suitable order. In addition, although each of the various features, techniques, configurations, etc. herein may be discussed in different parts of this disclosure, it is contemplated that each of the concepts can be implemented independently of one another or in combination with one another. Accordingly, the present invention can be embodied and considered in many different ways.

[0025] It should be noted that this Summary section does not define every embodiment and / or incrementally novel aspect of the present disclosure or claimed invention(s). Rather, this Summary merely provides a preliminary discussion of various embodiments and corresponding novel points over the prior art. For additional details and / or anticipated aspects of the present invention and embodiments, the reader is referred to the Detailed Description section and corresponding drawings of the present disclosure as further discussed below.

[0026] A more complete understanding of the present invention and its advantages may be obtained by reference to the following description taken in conjunction with the accompanying drawings, in which like reference numerals indicate like features, and in which: It should be pointed out, however, that the accompanying drawings merely illustrate exemplary embodiments of the disclosed concepts and are therefore not to be considered limiting in scope, as the disclosed concepts may admit of other equally effective embodiments. [Brief explanation of the drawings]

[0027] [Figure 1A] FIG. 1 is a process flow diagram illustrating an example process flow for forming an EUV-active photoresist film on a surface of a semiconductor substrate according to one embodiment of the present disclosure. [Figure 1B] Illustrated are example chemistries that can be used in the chemical polymer deposition and thermal treatment steps shown in FIG. 1A, including example metal precursors that can be used during a plasma process step to form an example non-solid organometallic oxide polymer layer on a substrate surface, and an example EUV-active photoresist film that can be formed during a subsequent thermal treatment step. [Figure 2A] FIG. 1 is a flow chart diagram illustrating one embodiment of a method for processing a semiconductor substrate according to the present disclosure. [Figure 2B] FIG. 10 is a flow chart diagram illustrating another embodiment of a method for processing a semiconductor substrate according to the present disclosure. [Figure 3]FIG. 1 is a process flow diagram illustrating an example process flow that can be used to form a film structure including a moisture barrier layer formed over an EUV-activated photoresist film in accordance with one embodiment of the present disclosure. [Figure 4] FIG. 1 is a process flow diagram illustrating an example process flow that can be used to form a film structure including a first hydrocarbon layer formed beneath an EUV-active photoresist film and a second hydrocarbon layer formed over the EUV-active photoresist film in accordance with another embodiment of the present disclosure. [Figure 5] FIG. 1 is a process flow diagram illustrating an example process flow that can be used to pattern a film structure containing a moisture barrier layer formed over an EUV-activated photoresist film, thus forming a patterned photoresist. [Figure 6A] FIG. 1 is a process flow diagram illustrating an example process flow that can be used to perform area selective deposition (ASD) using patterned photoresist in accordance with a first embodiment of the present disclosure. [Figure 6B] FIG. 1 is a process flow diagram illustrating an example process flow that can be used to perform area selective deposition (ASD) using patterned photoresist in accordance with a first embodiment of the present disclosure. [Figure 7] FIG. 10 is a process flow diagram illustrating an example process flow that can be used to perform area selective deposition (ASD) using patterned photoresist in accordance with a second embodiment of the present disclosure. [Figure 8] FIG. 10 is a process flow diagram illustrating an example process flow that can be used to perform area selective deposition (ASD) using patterned photoresist in accordance with a third embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0028] The present disclosure relates to photolithography processes, and more particularly to improved process flows and methods for forming a moisture barrier layer over an EUV-active photoresist film formed on a semiconductor substrate.

[0029] The present disclosure provides an improved process flow and method for forming an extreme ultraviolet (EUV)-active photoresist on a semiconductor substrate. The EUV-active photoresist film described herein can be a polymerized organometallic oxide (e.g., a metal alkoxy polymer film) having carbon-carbon bonds. The presence of carbon-carbon bonds increases the mechanical strength and photosensitivity of the EUV-active photoresist film compared to conventional photoresists used for EUV lithography.

[0030] Many EUV-activated photoresist films, including conventional metal oxide resist (MOR) films and metal alkoxy polymer films, are chemically and mechanically weak. For example, Sn-OC n H m Tin (Sn)-containing alkoxy polymer films containing Sn—OH or Sn—OH surface species readily absorb moisture from the air or from the processing environment. n H m The surface species can react with moisture in the ambient environment and undergo chemical reactions to form metal oxide-metal species (e.g., Sn—O—Sn species) on the exposed surface of the EUV-active photoresist film. This can adversely affect the material properties and quality of the EUV-active photoresist film during photolithography processing. Therefore, protecting the EUV-active photoresist film from moisture in the ambient environment can be very beneficial.

[0031] The present disclosure also provides an improved process flow and method for forming a moisture barrier layer over an EUV-active photoresist film. The EUV-active photoresist film can be an improved EUV-active photoresist film as further described herein or a conventional metal oxide resist (MOR) film. The moisture barrier layer protects the EUV-active photoresist by preventing or reducing the uptake of moisture and other contaminants on the surface of the EUV-active photoresist film. In some embodiments, the moisture barrier layer can be transparent to light used in lithographic processing and therefore can remain on the surface of the EUV-active photoresist film during lithographic processing.

[0032] Formation of EUV-active photoresist films Referring now to the drawings, FIG. 1A illustrates one embodiment of a process flow 100 used to form an EUV-active photoresist on a surface of a semiconductor substrate in accordance with one embodiment of the present disclosure. As shown in FIG. 1A, the process flow 100 begins by performing a low-temperature, low-ion energy plasma process 120 that exposes the surface of the semiconductor substrate 110 to a plasma-excited vapor 125 containing a metal precursor having a carbon-carbon double bond. In some embodiments, additional precursors may also be included in the plasma-excited vapor 125. Examples of suitable metal precursors and additional precursors are discussed in more detail below. During the plasma process 120, the semiconductor substrate 110 is maintained at a relatively low substrate temperature (e.g., a substrate temperature below about 100° C., more preferably below about 0° C.), while the ions in the plasma-excited vapor 125 are maintained at a relatively low ion energy (e.g., an ion energy of less than about 50 eV, more preferably between about 0 eV and about 5 eV). Under these conditions, a non-solid organometallic oxide polymer layer 135 is deposited onto the surface of the semiconductor substrate 110 by chemical vapor deposition polymerization (CVP) 130 .

[0033] Once the non-solid organometallic oxide polymer layer 135 is deposited onto the substrate surface, the semiconductor substrate 110 is subjected to a thermal treatment 140 (e.g., a thermal bake) to further polymerize the non-solid organometallic oxide polymer layer 135 and form an organometallic oxide polymer film 145 having carbon-carbon bonds on the substrate surface. The organometallic oxide polymer film 145 formed according to process flow 100 is an EUV-active photoresist film that can be patterned and developed with EUV lithography, as described in more detail below.

[0034] As described above, the plasma process 120 shown in FIG. 1A is performed at a relatively low substrate temperature and ion energy. According to one embodiment, the substrate temperature during plasma exposure can be, for example, less than about 100° C. In other embodiments, the substrate temperature during plasma exposure can be about −50° C. to about 0° C., about −50° C. to about −25° C., or about −25° C. to about 0° C. According to one embodiment, the ion energy of the ions in the plasma-excited vapor 125 can be about 50 eV. In other embodiments, the ion energy can be less than 50 eV, for example, about 0 eV to about 50 eV, or about 0 eV to about 5 eV. The use of an ion energy of about 0 eV to about 5 eV is believed to be beneficial for minimizing plasma damage to the non-solid organometallic oxide polymer layer 135 deposited on the substrate surface during the plasma process 120.

[0035] The plasma process 120 shown in FIG. 1A can be performed in a wide variety of plasma processing systems and / or chambers, including, but not limited to, the following: In some embodiments, the plasma process 120 can be performed in a capacitively coupled plasma (CCP) processing chamber or an inductively coupled plasma (ICP) processing chamber. In some examples, a CCP processing chamber having a source frequency between 13.56 MHz and 60 MHz and a source power between about 10 W and about 500 W can be used to generate plasma conditions including an ion energy of about 50 eV (or less). The gas pressure in the CCP processing chamber can range, for example, from about 100 mTorr to about 20 Torr. The substrate temperature, as described above, can be less than about 100° C.

[0036] In other embodiments, the plasma process 120 shown in FIG. 1A can be performed using a plasma processing system containing a remote plasma source. Examples of such plasma processing systems include the use of remote plasma sources using radio frequency (RF), very high frequency (VHF), and microwave frequency (MWF). A plasma processing system containing a remote plasma source can include (a) a vacuum chamber divided into a plasma space and a separate wafer space by a separator plate with multiple holes, or (b) a plasma source attached to the vacuum chamber. A remote plasma source can be desirable in some embodiments because it is effective in minimizing or eliminating exposure of the substrate to high-energy ions.

[0037] The thermal treatment 140 shown in FIG. 1 involves thermally treating the semiconductor substrate 110 containing the non-solid organometallic oxide polymer layer 135 formed thereon to further polymerize the non-solid organometallic oxide polymer layer 135 and form an organometallic oxide having polymerized carbon-carbon bonds. A variety of methods can be utilized to thermally treat the semiconductor substrate 110. According to one embodiment, the thermal treatment 140 step can be performed in a vacuum chamber at an elevated substrate temperature. In such an embodiment, the thermal treatment can be performed under reduced pressure in the presence of an additional gas, which can include, for example, hydrogen bromide (HBr), hydrogen (H), helium (He), argon (Ar), neon (Ne), xenon (Xe), nitrogen (N), and / or carbon monoxide (CO). In one example, the thermal treatment can be performed using a substrate holder functioning as a hot plate. Furthermore, the thermal treatment can be performed without plasma excitation or with plasma excitation of an additional gas. In another example, the thermal treatment can be performed by optical means, such as laser heating. According to one embodiment, the substrate temperature during the thermal treatment 140 step can be from about 0° C. to about 400° C. In other embodiments, the substrate temperature during the thermal treatment 140 step can be from about 0° C. to about 50° C., from about 50° C. to about 100° C., from about 100° C. to about 200° C., from about 200° C. to about 300° C., from about 0° C. to about 200° C., or from about 200° C. to about 400° C. Other methods for carrying out the polymerization shown in FIG. 1A include, but are not limited to, the use of a hot filament above the substrate or activation by e-beam, UV, EUV, high NA EUV, or next generation high NA / hyper NA EUV.

[0038] A wide variety of metal precursors can be used to form an EUV-active photoresist film during the plasma process 120 shown in FIG. 1A. For example, a metal precursor including an EUV metal can be used. In this disclosure, the term "EUV metal" can refer to a metal component having a high EUV absorption coefficient. According to one embodiment, the EUV metal can include tin (Sn). In other embodiments, the EUV metal can include zirconium (Zr), indium (In), antimony (Sb), bismuth (Bi), hafnium (Hf), or aluminum (Al). According to one embodiment, the organometallic oxide of the EUV-active photoresist film contains a central metal atom selected from the group consisting of tin (Sn), zirconium (Zr), indium (In), antimony (Sb), bismuth (Bi), zinc (Zn), hafnium (Hf), aluminum (Al), and combinations thereof. In the following description, various embodiments, including the figures, are described using tin (Sn) as the metal component to serve as an example for the EUV-active photoresist film. However, it is recognized that the metal component is not limited to tin (Sn) and that other metals may also be present in the EUV-active photoresist film.

[0039] According to one embodiment, the metal precursor contains tin (Sn) and has the formula Sn α O β (OC m H n )ΓC x H y (wherein m, n, and α are any integers equal to or greater than 1, β, Γ, x, and y are any integers equal to or greater than 0, and β and Γ are not simultaneously equal to 0). Examples include SnR1(O-R2)3, SnR12(O-R2) 2、 SnHR1(O-R2)2 (wherein R1: CH3, C2H3, C3H5, C4H7, or C6H6, and R2: CH3, C2H5, C3H7, or C4H9). Additional examples of tin (Sn)-containing metal precursors include SnCH3 t Bu(O- t Bu) 2、 Sn t Bu(O- t Bu)3, Sn tBu(O-C3H7)3, Sn t Bu(O-C2H5)3, Sn t Bu(O-CH3)3, SnCH3C2H3(O- t Examples of tin (Sn)-containing metal precursors include Sn(C2H4O2) and Sn(OR)2, where R can be selected from CH3, C2H5, and C4H9. Still other examples include a mixture of Sn(N(CH3)2)4 and HOCH2CH2OH.

[0040] According to another embodiment, the metal precursor contains tin (Sn) and has the formula Sn x C y H z where x, y, and z are any integers equal to or greater than 1. In one example, the metal precursor is selected from the group consisting of Sn(CH), Sn(C,H), SnH(CH), and SnH(C,H). In such an embodiment, the plasma-excited vapor 125 containing the metal precursor can further include an additional gas such as, but not limited to, hydrogen (H), helium (He), argon (Ar), neon (Ne), krypton (Kr), nitrogen (N), or acetylene (C,H).

[0041] According to yet another embodiment, the metal precursor contains a transition metal (M) and has the formula M α O β (OC m H n )ΓC x H y (wherein m, n, and α are any integers equal to or greater than 1, and β, Γ, x, and y are any integers equal to or greater than 0, and β and Γ are not simultaneously equal to 0.) Examples of transition metals with high EUV absorption coefficients include, but are not limited to, tin (Sn), antimony (Sb), indium (In), and bismuth (Bi).

[0042] In some embodiments, the plasma-excited vapor 125 can include a metal precursor and an additional precursor. For example, the metal precursor may contain tin (Sn) and have the formula Sn α O β (OC m H n )ΓC x H y , the additional precursor added to the plasma excited vapor 125 may contain tin (Sn) and have the formula Sn α C x H y wherein m, n, and α are any integers equal to or greater than 1. The metal precursor may contain a transition metal (M) and have the formula M α O β (OC m H n )ΓC x H y , additional precursors added to the plasma excited vapor 125 may contain a transition metal (M) and have the formula M α C x H y where m, n, and α are any integers equal to or greater than 1.

[0043] According to one embodiment, the photosensitivity of the EUV-active photoresist film to EUV radiation can be amplified with additional monomers by introducing chemical species having a carbon-oxygen double bond (C=O) surrounding the organometallic oxide. According to one embodiment, the plasma-excited vapor 125 can further contain additional monomers, such as hydrocarbons containing C=O bonds. For example, the plasma-excited vapor 125 can further contain additional monomers, such as ketones, aldehydes, or esters, each of which contains a carbonyl group having a carbon-oxygen double bond (C=O). The ketones can be selected from the group consisting of acetone, methyl ethyl ketone, methyl propyl ketone, and methyl isopropyl ketone. The aldehydes can be selected from the group consisting of formaldehyde, acetaldehyde, and propionaldehyde. The esters can be selected from the group consisting of ethyl methanoate, methyl acetate, ethyl acetate, methyl acrylate, methyl butanoate, and methyl salicylate.

[0044] According to one embodiment, the plasma-excited vapor 125 may include a tin (Sn)-containing metal precursor, and the additional monomer may include a ketone, an aldehyde, or an ester. According to one embodiment, the plasma-excited vapor 125 may further include an additional gas, such as, but not limited to, hydrogen (H), helium (He), argon (Ar), neon (Ne), xenon (Xe), nitrogen (N), carbon monoxide (CO), ammonia (NH), or hydrogen sulfide (HS).

[0045] FIG. 1B illustrates an example chemistry that can be used for the chemical polymer deposition and thermal treatment step shown in FIG. 1A , including an example metal precursor 127 that can be used in a plasma process 120 to form an example non-solid organometallic oxide polymer layer 135 on the surface of a semiconductor substrate 110. In FIG. 1B , the metal precursor 127 is an organotin compound containing a carbon-carbon double bond 129. Plasma excitation of the organotin compound affects the carbon-carbon double bond 129 to form a non-solid organometallic oxide polymer layer 135 on the surface of the semiconductor substrate 110. The plasma-based reaction forms liquid oligomeric units 137 of the organometallic oxide on the substrate surface. A subsequent thermal treatment step further polymerizes the liquid oligomeric units 137 of the non-solid organometallic oxide polymer layer 135 to form an organometallic oxide polymer film 145. As shown schematically in FIG. 1B, the liquid oligomeric units 137 of the non-solid organometallic oxide polymer layer 135 polymerize upon thermal treatment to form an EUV-active photoresist film comprising an organometallic oxide having a polymerized carbon-carbon backbone 146.

[0046] In the example embodiment shown in FIG. 1B, the EUV-active photoresist film is formed by plasma-excited SnCH(CH)(O-CH) precursor molecules to form a non-solid organometallic oxide polymer layer 135 on the surface of the semiconductor substrate 110, which is followed by thermal treatment of the semiconductor substrate 110 to form an organometallic oxide polymer film 145 having polymerized carbon-carbon bonds.

[0047] 1A can plasma-excite the SnCH(C2H3)(O-CH3)2 precursor molecules shown in FIG. 1B using a low-temperature, low-ion energy plasma process. During the plasma process 120, for example, the temperature of the semiconductor substrate 110 can be less than about 100°C, and the ion energy of the ions in the plasma-excited vapor 125 can be less than about 50 eV. In some embodiments, the SnCH(C2H3)(O-CH3)2 precursor molecules can be plasma-excited without the presence of an oxidizer, such as oxygen (O2), ozone (O3), water (H2O), hydrogen peroxide (H2O2), carbon dioxide (CO2), or carbon monoxide (CO). In some embodiments, the plasma excitation can include an additional gas, such as, for example, hydrogen (H), helium (He), argon (Ar), neon (Ne), krypton (Kr), nitrogen (N), acetylene (C2H2), or carbon monoxide (CO).

[0048] 1A may be performed in a vacuum chamber at an elevated substrate temperature, such as from about 0° C. to about 400° C. In some embodiments, the thermal treatment 140 step may be performed under reduced pressure in the presence of an additional gas, which may include, for example, hydrogen bromide (HBr), hydrogen (H), helium (He), argon (Ar), neon (Ne), xenon (Xe), nitrogen (N), and / or carbon monoxide (CO).

[0049] Chemical vapor deposition polymerization (CVP), shown in Figures 1A and 1B, i.e., plasma excitation of organotin compounds followed by thermal treatment of a semiconductor substrate, forms organometallic oxides with polymerized carbon-carbon bonds. As shown in Figure 1B, organotin compounds form C m H n It contains Sn-O- units protected by ligands (e.g., methane (CH3) and ethyl groups (C2H5)). m H nThe ligands prevent Sn-O-Sn cross-linking (which creates weak and unstable bonds that increase film density and reduce EUV light sensitivity) and instead provide stronger carbon-carbon bonds. Furthermore, the organotin compound containing carbon-carbon double bonds 129 promotes polymerization during the thermal treatment 140 step to form an organometallic oxide polymer film 145 with a polymerized carbon-carbon backbone 146, which enhances the mechanical strength and photosensitivity of the EUV-active photoresist film. In some embodiments, the photosensitivity of the EUV-active photoresist film can be further increased by adding a monomer to the plasma-excited vapor 125 (not shown in FIG. 1B ), where the additional monomer has a carbon-oxygen double bond (C═O) surrounding the organometallic oxide.

[0050] The EUV-active photoresists described above and illustrated in FIGS. 1A and 1B offer various advantages over conventional photoresists used for EUV lithography, such as chemically amplified resists (CARs) and vapor-deposited metal oxide-containing films. For example, the EUV-active photoresists disclosed herein have higher EUV absorbance and therefore better resist sensitivity compared to conventional CARs. In some embodiments, the higher EUV absorbance may allow for a reduction in the photoresist thickness required for acceptable performance. The EUV-active photoresists disclosed in the present disclosure may also exhibit better etch resistance than conventional CARs. In addition, the methods disclosed above may enable a uniform chemical composition of the EUV-active photoresist, which may be beneficial in mitigating issues of blurring or line edge roughness.

[0051] In addition to the CAR, the EUV-active photoresists disclosed herein offer various advantages over conventionally deposited metal oxide-containing vapor-deposited films, such as those described in the '004 patent. Unlike the conventional process disclosed in the '004 patent, in which a typical CVD / ALD process involves reacting various organotin oxide precursors with an oxidizing agent (e.g., carbon dioxide or carbon monoxide) to form a solid metal oxide-containing film on a semiconductor substrate, the method disclosed above uses a low-temperature, low-ion energy plasma process that exposes the substrate surface to a plasma-excited vapor containing a metal precursor having a carbon-carbon double bond to deposit a non-solid, organometallic oxide polymer layer (containing liquid oligomeric units) having carbon-carbon bonds onto the substrate surface. The carbon-carbon double bonds provided in the metal precursor promote polymerization during a subsequent thermal treatment step to form an organometallic oxide polymer film having carbon-carbon bonds. The presence of carbon-carbon bonds in organometallic oxide polymer films increases the mechanical strength and stability of the EUV-active photoresist films disclosed herein compared to conventionally deposited metal oxide-containing films containing Sn—OH and Sn—O—Sn bonds.

[0052] As mentioned above, many EUV-active photoresist films (including conventional metal oxide resist (MOR) films and the metal alkoxy polymer films shown above in FIGS. 1A and 1B) are chemically and mechanically weak and prone to absorbing moisture from the ambient environment. In the present disclosure, a moisture barrier is formed on the EUV-active photoresist film to prevent the EUV-active photoresist film from absorbing moisture from the ambient environment and chemically reacting with the moisture to form metal oxide-metal species on the surface of the EUV-active photoresist film. The EUV-active photoresist film can be an EUV-active photoresist film or a conventional metal oxide resist (MOR) film, as shown above in FIGS. 1A-1B.

[0053] Method for processing a semiconductor substrate 2A and 2B illustrate various embodiments of methods for processing a semiconductor substrate in accordance with the present disclosure. More specifically, FIGS. 2A and 2B illustrate a method that can be used to form a moisture barrier layer on an EUV-active photoresist film and subsequently pattern the EUV-active photoresist film with EUV lithography. It will be appreciated that the embodiments shown in FIGS. 2A and 2B serve as examples only, and that additional methods may utilize the techniques described herein. Furthermore, additional processing steps may be added to the methods shown in FIGS. 2A and 2B, as the steps described are not intended to be exclusive. Furthermore, the order of the steps is not limited to the order shown in the figures, as different orders may occur and / or various steps may be performed in combination or simultaneously.

[0054] 2A illustrates one embodiment of a method 200 according to the present disclosure. According to one embodiment, the method 200 shown in FIG. 2A includes forming an EUV-active photoresist film on a surface of a semiconductor substrate (in step 210), plasma-depositing a moisture barrier layer containing a hydrocarbon polymer on the EUV-active photoresist film (in step 220), and patterning the EUV-active photoresist film with EUV lithography to form a patterned photoresist on the surface of the semiconductor substrate (in step 230). Providing a moisture barrier layer over the EUV-active photoresist film prevents the EUV-active photoresist film from reacting with the ambient environment and forming metal oxide-metal species on the surface of the EUV-active photoresist film, which would degrade the material properties and quality of the EUV-active photoresist film during lithography processing.

[0055] 2B illustrates another embodiment of a method 250 according to the present disclosure. According to one embodiment, the method 250 shown in FIG. 2B includes plasma depositing (in step 205) a first hydrocarbon polymer layer on a surface of a semiconductor substrate, followed by plasma depositing (in step 215) an EUV-active photoresist film on the first hydrocarbon polymer layer. After depositing the EUV-active photoresist film, the method 250 further includes plasma depositing (in step 225) a second hydrocarbon polymer layer on the EUV-active photoresist film and patterning (in step 230) the EUV-active photoresist film with EUV lithography to form a patterned photoresist on the surface of the semiconductor substrate. Providing the first hydrocarbon polymer layer below the EUV-active photoresist film prevents the EUV-active photoresist film from reacting with the underlying silicon-containing substrate and forming metal oxide-silicon species that are difficult to remove during subsequent processing steps. In the embodiment shown in FIG. 2, the second hydrocarbon polymer layer deposited on the EUV-active photoresist film in step 225 is a moisture barrier layer, as described above.

[0056] In some embodiments, the EUV-active photoresist film formed in steps 210 and 215 can be an organic metal oxide or a metal oxide resist (MOR). In some embodiments, the EUV-active photoresist film formed in steps 210 and 215 can be an organic metal oxide having polymerized carbon-carbon bonds, as described above and shown in FIGS. 1A and / or 1B. In one example, the EUV-active photoresist film can be an organic metal oxide containing tin (Sn). In another example, the EUV-active photoresist film can be an organic metal oxide containing zirconium (Zr), indium (In), antimony (Sb), bismuth (Bi), zinc (Zn), hafnium (Hf), aluminum (Al), or a combination thereof. In some embodiments, the EUV-active photoresist film can be formed in steps 210 and 215 by (a) exposing the surface of a semiconductor substrate to a plasma-excited vapor containing a metal precursor having a carbon-carbon double bond to form a non-solid organometallic oxide polymer layer on the surface of the semiconductor substrate, as described above and illustrated in FIG. 1A , and (b) thermally treating the semiconductor substrate to further polymerize the non-solid organometallic oxide polymer layer to form an organometallic oxide having polymerized carbon-carbon bonds. The EUV-active photoresist film formed in steps 210 and 215 can have a wide variety of thicknesses. For example, in some embodiments, the thickness of the EUV-active photoresist film (e.g., organometallic oxide having polymerized carbon-carbon bonds) can range from about 3 nm to about 5 nm.

[0057] The first hydrocarbon polymer layer deposited in step 205 and the second hydrocarbon polymer layer (i.e., moisture barrier layer) deposited in steps 220 and 225 can contain a wide variety of hydrocarbon polymers. In some embodiments, the hydrocarbon polymer can include carbon and hydrogen. In example embodiments, the hydrocarbon polymer can include a) carbon, hydrogen, and oxygen; b) carbon, hydrogen, oxygen, and nitrogen; or c) carbon, hydrogen, and nitrogen. The first and second hydrocarbon polymer layers can be formed in steps 205, 220, and 225 by plasma-exciting a wide variety of precursors. For example, a hydrocarbon precursor, an aldehyde precursor, and / or an amine precursor can be plasma-excited to form one or more of the first and second hydrocarbon polymer layers. Examples of suitable precursors are discussed in more detail below.

[0058] The first hydrocarbon polymer layer deposited in step 205 and the second hydrocarbon polymer layer (i.e., moisture barrier layer) deposited in steps 220 and 225 can also be formed having a wide range of thicknesses. For example, the thickness of the moisture barrier layer deposited in step 220 and the second hydrocarbon polymer layer deposited in step 225 can be greater than 1 nm. If the first hydrocarbon polymer layer is utilized directly underneath an EUV-active photoresist film, the thickness of the first hydrocarbon polymer layer can also be greater than about 1 nm.

[0059] In some embodiments, a relatively thin (e.g., about 1 nm to 10 nm) moisture barrier layer / second hydrocarbon polymer layer may be deposited in steps 220 and 225. In some embodiments, the EUV-active photoresist film may be patterned in step 230 by (a) exposing the moisture barrier layer and the EUV-active photoresist film to EUV radiation, whereby areas of the EUV-active photoresist film exposed to EUV radiation are converted to reacted photoresist, while areas of the EUV-active photoresist not exposed to EUV radiation remain unreacted; (b) removing the moisture barrier layer; and (c) removing specific areas of the EUV-active photoresist to form a photoresist pattern. In some embodiments, the patterning step may remove unreacted areas of the EUV-active photoresist to form a first photoresist pattern (e.g., negative photoresist) on the substrate. In some embodiments, method 200 / 250 may further include selectively depositing a material film on top of the first photoresist pattern relative to the exposed surface of the semiconductor substrate. In some embodiments, the patterning step may remove reacted areas of the EUV-active photoresist to form a second photoresist pattern (e.g., a positive photoresist) on the substrate. In some embodiments, method 200 / 250 may further include selectively depositing a material film on the exposed surface of the semiconductor substrate relative to the second photoresist pattern.

[0060] In other embodiments, a relatively thick (e.g., greater than 10 nm) moisture barrier layer / second hydrocarbon polymer layer may be deposited in steps 220 and 225. In some embodiments, the EUV-active photoresist film may be patterned in step 230 by (a) exposing the moisture barrier layer to EUV radiation, wherein the regions of the moisture barrier layer exposed to EUV radiation are converted to a reacted moisture barrier layer and the regions of the moisture barrier layer not exposed to EUV radiation remain unreacted, (b) removing the regions of the reacted moisture barrier layer to form a patterned moisture barrier layer, and (c) exposing the EUV-active photoresist film to EUV radiation through the openings in the patterned moisture barrier layer, wherein the regions of the EUV-active photoresist film exposed to EUV radiation are converted to a reacted photoresist and the regions of the EUV-active photoresist not exposed to EUV radiation remain unreacted. In some embodiments, method 200 / 250 may further include selectively depositing a material film on top of the reacted photoresist and removing the patterned moisture barrier layer. The patterned moisture barrier layer may be removed before or after the material film is selectively deposited on top of the reacted photoresist.

[0061] Formation of a film structure containing a moisture barrier layer and an EUV-active photoresist film 2A and 2B, a moisture barrier layer is formed on the EUV-active photoresist film to prevent the EUV-active photoresist film from absorbing moisture from the ambient environment and chemically reacting with the moisture to form metal oxide-metal species on the surface of the EUV-active photoresist film. When a tin (Sn)-containing organometallic oxide is used as the EUV-active photoresist film, the moisture barrier layer prevents Sn-O-Sn species from forming on the surface of the EUV-active photoresist film. By protecting the EUV-active photoresist film from the ambient environment, the moisture barrier layer described herein increases the mechanical strength and stability of the EUV-active photoresist film.

[0062] 3 illustrates an example process flow 300 that can be used to form a film structure including a moisture barrier layer 330 formed on an EUV-active photoresist film 315, according to one embodiment of the present disclosure. For example, as shown in process flow 100 of FIG. 1A , after forming the EUV-active photoresist film 315 on the surface of a semiconductor substrate 310, the moisture barrier layer 330 is deposited on the top surface of the EUV-active photoresist film 315 using plasma excitation of precursors above the substrate surface. In some embodiments, the moisture barrier layer 330 can be plasma deposited on the EUV-active photoresist film 315 by performing a plasma process 320 that exposes the surface of the EUV-active photoresist film 315 to a plasma-excited vapor 325 containing at least one precursor. As described in more detail below, a wide variety of precursors can be used to form the moisture barrier layer 330. By providing a film structure that includes a moisture barrier layer 330 formed over the EUV-activated photoresist film 315, the process flow 300 shown in FIG. 3 prevents the EUV-activated photoresist film 315 from reacting with the ambient environment and forming undesirable forms of metal oxide-metal species on the surface of the photoresist film.

[0063] 4 illustrates another example of a process flow 400 that can be used to form a film structure including a moisture barrier layer 330 formed on an EUV-active photoresist film 315 according to another embodiment of the present disclosure. In the embodiment shown in FIG. 4 , a first hydrocarbon polymer layer 420 is plasma-deposited on the surface of the semiconductor substrate 310 by performing a first plasma process 410 that exposes the surface of the semiconductor substrate 310 to plasma-activated vapor 415 containing at least one precursor. An EUV-active photoresist film 315 is then deposited on the first hydrocarbon polymer layer 420 using, for example, the process flow 100 shown in FIG. 1A . After forming the EUV-active photoresist film 315, a moisture barrier layer 330 is deposited on the EUV-active photoresist film 315 by performing a second plasma process 430 that exposes the surface of the EUV-active photoresist film 315 to plasma-activated vapor 435 containing at least one precursor. In some embodiments, the moisture barrier layer 330 deposited onto the EUV-active photoresist film 315 may be a second hydrocarbon polymer layer, as described above. A wide variety of precursors may be used to form the first hydrocarbon polymer layer 420 and the moisture barrier layer 330 (e.g., the second hydrocarbon polymer layer), as described in more detail below.

[0064] In some embodiments, the semiconductor substrate 310 may be a silicon (Si)-containing substrate (e.g., SiC), and the first hydrocarbon polymer layer 420 may be deposited onto the substrate surface to reduce or prevent chemical reactions between the EUV-active photoresist film 315 (e.g., Sn-based photoresist) and the underlying Si-containing substrate. For example, the Sn-based photoresist may react with the Si-containing substrate to form Sn—O—Si species on the substrate surface, which may be difficult to remove during a subsequent development step performed to remove unreacted areas of the EUV-active photoresist film (i.e., areas of the EUV-active photoresist that were not exposed to EUV radiation during the EUV lithography step). By providing a film structure including a first hydrocarbon polymer layer 420 formed beneath the EUV-active photoresist film 315 and a second hydrocarbon polymer layer (e.g., moisture barrier layer 330) formed over the EUV-active photoresist film 315, the process flow 400 shown in FIG. 4 further prevents the EUV-active photoresist film 315 from reacting with the underlying substrate and forming undesirable forms of metal oxide-silicon species on the surface of the substrate.

[0065] A wide variety of precursors can be utilized in the plasma process 320 shown in Figure 3 and the first plasma process 410 and second plasma process 430 shown in Figure 4 to form a hydrocarbon polymer layer. In some embodiments, for example, a hydrocarbon precursor can be used to form a hydrocarbon polymer layer. The hydrocarbon precursor can be a compound of formula C α H β where α is an integer equal to or greater than 1, and β is any integer equal to or greater than 1. α H βNon-limiting examples of hydrocarbon precursors having the formula (I) include, but are not limited to, methyl (CH), acetylene (C2H2), ethylene (C2H4), propyl (C3H7), and styrene (C6H5CH=CH2). In some embodiments, the plasma excitation can further include an additional gas, such as, for example, hydrogen (H2), helium (He), argon (Ar), neon (Ne), xenon (Xe), nitrogen (N2), carbon monoxide (CO), ammonia (NH3), or hydrogen sulfide (HS).

[0066] Another example of a precursor that can be used to form the hydrocarbon polymer layer is a compound of formula C α H β O γ wherein α is an integer equal to or greater than 1, β is any integer equal to or greater than 1, and γ is any integer equal to or greater than 1. α H β O γ An example of an aldehyde precursor having the formula (I) includes benzaldehyde (CHCHO). In some embodiments, the plasma excitation can further include an additional gas, such as hydrogen (H), helium (He), argon (Ar), neon (Ne), xenon (Xe), nitrogen (N), carbon monoxide (CO), ammonia (NH), or hydrogen sulfide (HS).

[0067] In yet another example, an amine precursor may be used to form the hydrocarbon polymer layer, the amine precursor having the formula C α H β N γ O δ (wherein α is an integer of 1 or more, β is any integer of 1 or more, γ is any integer of 1 or more, and δ is an integer of 0 or more). α H β N γ O δAn example of an amine precursor having the formula (I) includes phenylenediamine (C6H4(NH2)2). In some embodiments, the plasma excitation can further include an additional gas, such as hydrogen (H2), helium (He), argon (Ar), neon (Ne), xenon (Xe), nitrogen (N2), carbon monoxide (CO), ammonia (NH3), or hydrogen sulfide (HS).

[0068] In the examples provided above, hydrocarbon precursors, aldehyde precursors, and / or amine precursors may be used to form the hydrocarbon polymer layer. In further examples, mixtures or combinations of precursors may be used to form the hydrocarbon polymer layer. For example, the hydrocarbon polymer layer may be formed using a C α H β O γ Precursor and C α H β N γ O δ It can be formed using a mixture with a precursor.

[0069] In some embodiments, the plasma process 320 shown in FIG. 3 and the first and second plasma processes 410 and 430 shown in FIG. 4 can be performed at relatively low substrate temperatures and ion energies. According to one embodiment, the substrate temperature during plasma excitation of the precursors used to form the hydrocarbon polymer layer can be, for example, less than about 100°C. For example, the substrate temperature during plasma exposure can be about −50°C to about 0°C, about −50°C to about −25°C, or about −25°C to about 0°C. According to one embodiment, the ion energy of the ions in the plasma-excited vapor 325, plasma-excited vapor 415, and / or plasma-excited vapor 435 can be about 50 eV. In other embodiments, the ion energy can be less than 50 eV, for example, about 0 eV to about 50 eV, or about 0 eV to about 5 eV.

[0070] A wide variety of plasma processing systems and / or chambers can be utilized to perform the plasma process 320 shown in FIG. 3 and the first and second plasma processes 410 and 430 shown in FIG. 4, including, but not limited to, the following processing chambers: In some embodiments, one or more of the plasma processes 320, 410, and 430 can be performed in a capacitively coupled plasma (CCP) processing chamber or an inductively coupled plasma (ICP) processing chamber. In some examples, a CCP processing chamber having a source frequency between 13.56 MHz and 60 MHz and a source power between about 10 W and about 500 W can be used to generate plasma conditions including an ion energy of about 50 eV (or less). The gas pressure in the CCP processing chamber can be, for example, between about 100 mTorr and about 20 Torr. The substrate temperature, as described above, can be less than about 100°C.

[0071] In other embodiments, one or more of the plasma processes 320, 410, and 430 can be performed using a plasma processing system containing a remote plasma source. Examples of such plasma processing systems include the use of remote plasma sources that use radio frequency (RF), very high frequency (VHF), and microwave frequency (MWF). A plasma processing system containing a remote plasma source can include (a) a vacuum chamber divided into a plasma space and a separate wafer space by a separator plate with multiple holes, or (b) a plasma source attached to the vacuum chamber. A remote plasma source can be desirable in some embodiments because it is effective in minimizing or eliminating exposure of the substrate to high-energy ions.

[0072] Patterning of film structures containing moisture barrier layers and EUV-active photoresist films Figure 5 illustrates an example process flow 500 that can be used to pattern a film structure containing a moisture barrier layer formed on an EUV-activated photoresist film. Although process flow 500 is shown patterning the film structure shown in Figure 3, the patterning process described herein is not strictly limited to the film structure shown in Figure 3 and can be applied to other film structures, such as, for example, the film structure shown in Figure 4.

[0073] In some embodiments, the process flow 500 may begin by forming a film structure 510 containing an EUV-active photoresist film 315 formed on a semiconductor substrate 310 and a moisture barrier layer 330 formed on the EUV-active photoresist film 315, as described above and shown in FIG. 3 . In the embodiment shown in FIG. 5 , the film structure 510 includes a relatively thin moisture barrier layer 330 having a thickness of, for example, less than about 10 nm. The relatively thin moisture barrier layer 330 formed above the EUV-active photoresist film 315 is at least partially transparent to EUV radiation. This allows EUV radiation to pass through the moisture barrier layer 330 and reach the EUV-active photoresist film 315 during a subsequent EUV lithography process to pattern the EUV-active photoresist film 315.

[0074] In other embodiments (not shown in FIG. 5), the moisture barrier layer 330 may be thick enough to absorb all or most of the EUV radiation, resulting in little or no EUV radiation reaching the EUV-active photoresist film 315 during a subsequent EUV lithography process. In such embodiments, a first EUV lithography process may be performed to pattern the moisture barrier layer 330, followed by a second EUV lithography process to pattern the portion of the EUV-active photoresist film 315 underlying the moisture barrier layer pattern, as shown, for example, in FIG.

[0075] After forming the film structure 510 containing the moisture barrier layer 330 and the EUV-active photoresist film 315, the process flow 500 shown in FIG. 5 performs an EUV lithography process in an EUV exposure 520 step, exposing the film structure 510 to EUV radiation 525 (e.g., at a wavelength of 13.5 nm). In other embodiments (not shown in FIG. 5), the moisture barrier layer 330 can be removed prior to exposure to EUV radiation, as shown, for example, in FIG. 8. The EUV lithography process can utilize a photomask (not shown in FIG. 5) such that the photo-induced reaction occurs only in regions 522 of the EUV-active photoresist film 315 exposed to EUV radiation 525. The regions 522 of the EUV-active photoresist film 315 exposed to EUV radiation 525 are converted to reacted photoresist. The regions 524 of the EUV-active photoresist film 315 not exposed to EUV radiation 525 remain unreacted. After the EUV exposure 520 step, an optional thermal treatment step (e.g., post-exposure bake (PEB)) 530 may be performed to stabilize the photoresist after EUV exposure by completing reactions initiated during exposure. In some embodiments, the optional thermal treatment step 530 may prevent changes in line edge roughness (LER), line width roughness (LWR), and / or critical dimension (CD).

[0076] After completing the EUV exposure 520 and optional post-exposure bake (PEB) 530, a development step 540 may be performed to remove the moisture barrier layer 330 and portions of the EUV-active photoresist film for patterning, thereby providing a patterned photoresist (or photoresist pattern) on the substrate surface. The development step 540 may be a wet or dry process. In some embodiments, a wet process may be used in the development step 540. For example, portions of the EUV-active photoresist may be removed by treating the substrate with a developer to (a) dissolve the reacted regions 522 of the EUV-active photoresist film 315 to provide a positive-tone photoresist 550, or (b) dissolve the unreacted regions 524 of the EUV-active photoresist film 315 to provide a negative-tone photoresist 560. Alternatively, in other embodiments, a dry process may be used to remove the reacted or unreacted regions of the EUV-active photoresist. A dry process may include, for example, a selective plasma etch process or a thermal process, advantageously eliminating the use of a developer. In certain embodiments, the dry process may be performed using a reactive ion etching (RIE) process or atomic layer etching (ALE).

[0077] Area-selective deposition on patterned photoresist In some embodiments, one or more of the patterned photoresists formed in FIG. 5 can be utilized for area selective deposition (ASD) of a material film. FIG. 6A illustrates one example of a process flow 600 that can be used for selective film deposition of a material film onto a photoresist pattern containing reacted photoresist (or negative photoresist 560). After forming negative photoresist 560 as shown in FIG. 5, process flow 600 shown in FIG. 6A utilizes area selective deposition (ASD) 610 to preferentially deposit a material film 620 onto the top surface of the reacted photoresist relative to the exposed surface of the semiconductor substrate 310. In other embodiments (not shown in FIG. 6A), selective deposition can instead be achieved by using a blocking layer on the reacted photoresist and depositing a material film onto the exposed surface of the underlying semiconductor substrate 310.

[0078] Figure 6B illustrates one example of a process flow 650 that can be used for selective film deposition onto a photoresist pattern containing unreacted photoresist (or positive photoresist 550). After forming positive photoresist 550 as shown in Figure 5, the process flow 650 shown in Figure 6B utilizes area selective deposition (ASD) 610 to preferentially deposit a material film 620 onto the exposed surface of the semiconductor substrate 310 relative to the top surface of the unreacted photoresist. The unreacted photoresist is then removed from the semiconductor substrate 310, leaving the deposited material film 620 on the substrate surface.

[0079] 7 illustrates another example of a process flow 700 that can be used to perform area selective deposition (ASD) using patterned photoresist in accordance with a second embodiment of the present disclosure. Although process flow 700 is shown patterning the film structure shown in FIG. 3, the processes described herein are not strictly limited to the film structure shown in FIG. 3 and can be applied to other film structures, such as, for example, the film structure shown in FIG. 4.

[0080] 3, by forming a film structure 710 containing an EUV-active photoresist film 315 formed on a semiconductor substrate 310 and a moisture barrier layer 330 formed on the EUV-active photoresist film 315. In the embodiment shown in FIG. 7, the film structure 710 includes a relatively thick moisture barrier layer 330 having a thickness of greater than about 10 nm, for example. The moisture barrier layer 330 may be thick enough to absorb all or most of the EUV radiation, resulting in little or no EUV radiation reaching the EUV-active photoresist film 315 during a subsequent EUV lithography process.

[0081] After forming the film structure 710 containing the moisture barrier layer 330 and the EUV-active photoresist film 315, the process flow 700 shown in FIG. 7 performs an EUV lithography process in which the film structure 710 is exposed to EUV radiation 725 (e.g., at a wavelength of 13.5 nm) in a first EUV exposure 720 step. In this embodiment, the moisture barrier layer 330 formed above the EUV-active photoresist film 315 is sufficiently thick and / or chemically tailored to absorb all or most of the EUV radiation 725, resulting in little or no EUV radiation reaching the EUV-active photoresist film 315. The EUV lithography process may utilize a photomask (not shown in FIG. 7 ) so that a photo-induced reaction occurs only in regions 722 of the moisture barrier layer 330 exposed to the EUV radiation 725. The regions 722 of the moisture barrier layer 330 exposed to the EUV radiation 725 are converted into a reacted moisture barrier layer. Areas 724 of the moisture barrier layer 330 that were not exposed to EUV radiation 725 remain unreacted. After the first EUV exposure 720 step, an optional thermal treatment step (e.g., a post-exposure bake (PEB)) 730 may be performed to stabilize the reacted moisture barrier layer after EUV exposure by completing the reactions initiated during the exposure.

[0082] After completing the first EUV exposure 720 and optional post-exposure bake (PEB) 730, a development step 740 may be performed to remove portions of the moisture barrier layer for patterning. The development step 740 may be a wet or dry process. The resulting pattern includes either the reacted or unreacted moisture barrier layer and exposes portions of the underlying EUV-activated photoresist film 315. In some embodiments, a wet process may be used in the development step 740. For example, portions of the moisture barrier layer may be removed by treating the substrate with a developer to either (a) dissolve the reacted regions 722 of the moisture barrier layer 330 or (b) dissolve the unreacted regions 724 of the moisture barrier layer 330 to form a moisture barrier layer pattern. FIG. 7 shows an embodiment in which the resulting moisture barrier layer pattern 726 includes the unreacted regions 724 of the moisture barrier layer 330. Alternatively, in other embodiments, a dry process may be used to remove the reacted or unreacted regions of the moisture barrier layer. Dry processes may include, for example, selective plasma etch processes or thermal processes, which advantageously eliminate the use of developers. In certain embodiments, dry processes may be performed using reactive ion etching (RIE) processes or atomic layer etching (ALE).

[0083] 7 may then expose the film structure 710 to EUV radiation 755 (e.g., at a wavelength of 13.5 nm) in a second EUV exposure 750 step. The second EUV lithography process exposes the EUV-active photoresist film 315 to EUV radiation 755 through the openings in the moisture barrier layer pattern 726. In the second EUV exposure 750 step, only regions 752 of the EUV-active photoresist film 315 exposed by the moisture barrier layer pattern 726 are exposed to EUV radiation 755 and converted into reacted photoresist. Regions 754 of the EUV-active photoresist 315 not exposed to EUV radiation 755 remain unreacted.

[0084] After patterning the EUV-activated photoresist film 315 to form a reacted photoresist, the process flow 700 shown in Figure 7 utilizes area selective deposition (ASD) 760 to preferentially deposit a material film 765 on top of the photoresist that has reacted to the moisture barrier layer pattern 726. A development step 770 may then be performed to remove the moisture barrier layer pattern 726 from the substrate, leaving the deposited material film 765 on the substrate. In other embodiments (not shown in Figure 7), the moisture barrier layer pattern 726 may be removed before area selective deposition (ASD) 760 of the material film 765.

[0085] 8 illustrates yet another example of a process flow 800 that can be used to perform area selective deposition (ASD) using patterned photoresist in accordance with a third embodiment of the present disclosure. As with the previous embodiment, the film structure shown in FIG. 3 is depicted in process flow 800. As with the previous embodiment, process flow 800 is not strictly limited to the film structure shown in FIG. 3 and can be applied to other film structures shown in FIG. 3, such as the film structure shown in FIG. 4.

[0086] 3, process flow 800 may begin by forming a film structure 810 containing an EUV-active photoresist film 315 formed on a semiconductor substrate 310 and a moisture barrier layer 330 formed on the EUV-active photoresist film 315. Unlike the previous embodiment, the moisture barrier layer 330 is removed prior to EUV exposure in the embodiment shown in FIG.

[0087] After the moisture barrier layer 330 is removed, the process flow 800 shown in FIG. 8 performs an EUV lithography process in an EUV exposure 820 step, exposing the EUV-active photoresist film 315 to EUV radiation 825 (e.g., at a wavelength of 13.5 nm). The EUV lithography process may utilize a photomask (not shown in FIG. 8 ) so that a light-induced reaction occurs only in regions 822 of the EUV-active photoresist film 315 exposed to the EUV radiation 825. The regions 822 of the EUV-active photoresist film 315 exposed to the EUV radiation 825 are converted to reacted photoresist. The regions 824 of the EUV-active photoresist film 315 not exposed to the EUV radiation 825 remain unreacted. After the EUV exposure 820 step, an optional thermal treatment step (e.g., post-exposure bake (PEB)) 830 may be performed to stabilize the reacted photoresist after EUV exposure by completing the reaction initiated during exposure. After patterning the EUV-activated photoresist film 315 to form reacted photoresist, the process flow 800 shown in FIG. 8 utilizes area selective deposition (ASD) 840 to preferentially deposit a material film 845 on top of the reacted photoresist relative to the unreacted photoresist.

[0088] A wide variety of material films can be selectively deposited in the process flows shown in Figures 6A, 6B, 7, and 8. In some embodiments, dielectric materials such as, for example, silicon oxide (SiO), silicon nitride (SiN), titanium oxide (TiO), zirconium oxide (ZrO), hafnium oxide (HfO), etc. can be selectively deposited in one or more of the process flows shown in Figures 6A, 6B, 7, and 8. In other embodiments, metallic materials such as, for example, titanium nitride (TiN), ruthenium (Ru), etc. can be selectively deposited in the above process flows.

[0089] The present disclosure provides various embodiments of improved processes and methods for forming EUV-active photoresist films containing organometallic oxides polymerized through carbon-carbon bonds for use in EUV photolithography processes. The process flow and methods disclosed herein improve upon conventional methods for forming EUV-active photoresists by utilizing chemical vapor deposition polymerization (CVP) to deposit metal oxide resist complexes on substrate surfaces using a low-temperature, low-ion energy plasma process. The low-temperature, low-ion energy plasma process uses various metal precursors with carbon-carbon double bonds to form liquid oligomeric units on the substrate surface, which further polymerize upon thermal treatment to form novel organometallic compounds with improved mechanical strength and stability compared to conventional EUV-active photoresists. Using the process flow and methods disclosed herein, the novel organometallic compounds are formed with excellent uniformity and better nucleation on underlying surfaces (even hydrophobic surfaces). The process flows and methods disclosed herein also provide for more rapid deposition on hydrophobic surfaces by using CVP to deposit liquid oligomeric units onto the substrate surface, instead of depositing hard metal oxide films using traditional CVD or ALD. Although the novel organometallic compounds described herein can be deposited at a wide variety of thicknesses (e.g., from less than 10 nm to hundreds of nm), the process flows and methods disclosed herein can enable the deposition of thinner, more uniform photoresist coatings onto the substrate surface, which can then be used to transfer sub-10 nm features into underlying layers of the substrate.

[0090] Additionally, the present disclosure provides various embodiments of improved process flows and methods for protecting EUV-active photoresist films by providing hydrocarbon polymer layers above and / or below the EUV-active photoresist film. The hydrocarbon polymer layer formed above the EUV-active photoresist film functions as a moisture control / barrier layer that prevents the EUV-active photoresist film from chemically reacting with moisture in the ambient environment and forming undesired metal oxide-metal species on the surface of the photoresist. The hydrocarbon polymer layer formed below the EUV-active photoresist film prevents the EUV-active photoresist film from chemically reacting with the underlying silicon substrate and forming undesired metal oxide-silicon species on the substrate surface. Thus, the hydrocarbon polymer layers described herein improve the performance of EUV-active photoresist films by preventing undesired reactions on the top and bottom surfaces of the photoresist.

[0091] The term "substrate" as used herein means and includes a base material or substructure upon which a material is formed. It will be understood that a substrate can include a single material, multiple layers of different materials, one or more layers having regions of different materials or structures therein, etc. These materials can include semiconductors, insulators, conductors, or combinations thereof. For example, a substrate can be a semiconductor substrate, a base semiconductor layer on a support structure, a metal electrode, or a semiconductor substrate having one or more layers, structures, or regions formed thereon. A substrate can be a conventional silicon substrate or other bulk substrate including a layer of a semiconducting material. As used herein, the term "bulk substrate" means and includes not only silicon wafers, but also silicon-on-insulator ("SOI") substrates, such as silicon-on-sapphire ("SOS") substrates and silicon-on-glass ("SOG") substrates, epitaxial layers of silicon on a base semiconductor substrate, and other semiconductor or optoelectronic materials, such as silicon germanium, germanium, gallium arsenide, gallium nitride, and indium phosphide. The substrate may be doped or undoped.

[0092] Substrate may also include any material portion or structure of a device, particularly a semiconductor device or other electronic device, and may be a base substrate structure such as a semiconductor substrate or a layer on or located on the base substrate structure. Thus, the term "substrate" is not intended to be limited to any particular base structure, underlying or overlying layer, patterned or unpatterned layer, but rather is intended to include any such layer or base structure, and any combination of layers and / or base structures.

[0093] It is noted that throughout this specification, references to "one embodiment" or "an embodiment" mean that a particular feature, structure, material, or characteristic described in connection with this embodiment is included in at least one embodiment of the invention, but do not mean that it is present in every embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification do not necessarily refer to the same embodiment of the invention. Furthermore, particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. Other embodiments may include various additional layers and / or structures and / or omit described features.

[0094] Those skilled in the art will recognize that various embodiments may be practiced without one or more of the specific details, or with other alternative and / or additional methods, materials, or components. In other instances, well-known structures, materials, or operations have not been shown or described in detail to avoid obscuring aspects of various embodiments of the invention. Similarly, for purposes of explanation, specific numbers, materials, and configurations are set forth to provide a thorough understanding of the invention. Nevertheless, the invention may be practiced without the specific details. Furthermore, it is understood that the various embodiments shown in the figures are illustrative representations and are not necessarily drawn to scale.

[0095] Further modifications and alternative embodiments of the methods described herein will be apparent to those skilled in the art in view of this description. It will therefore be appreciated that the described methods are not limited by these example configurations. It is to be understood that the forms of the methods shown and described herein are to be construed as example embodiments. Various modifications may be made in implementations. Thus, although the present invention has been described herein with reference to specific embodiments, various modifications and changes can be made without departing from the scope of the present invention. Accordingly, the specification and drawings should be regarded in an illustrative rather than a restrictive sense, and such modifications are intended to be included within the scope of the present invention. Furthermore, any benefits, advantages, or solutions to problems described herein with reference to particular embodiments are not intended to be construed as critical, necessary, or essential features or elements of any or all of the claims.

Claims

1. A method for processing a semiconductor substrate, wherein the method is Forming an extreme ultraviolet (EUV) activated photoresist film on the surface of the semiconductor substrate, Plasma deposition of a moisture barrier layer containing a hydrocarbon polymer onto the EUV-activated photoresist film, wherein the moisture barrier layer is either permeable to EUV rays or reactive to EUV rays, and the plasma deposition is performed accordingly. A method comprising patterning the EUV-activated photoresist film using EUV lithography to form a patterned photoresist on the surface of the semiconductor substrate.

2. The method according to claim 1, wherein forming the EUV-activated photoresist film comprises forming the EUV-activated photoresist film on the surface of the semiconductor substrate using chemical vapor deposition (CVP), and the EUV-activated photoresist film comprises an organometallic oxide having polymerized carbon-carbon bonds.

3. The method according to claim 1, wherein the hydrocarbon polymer comprises a) carbon and hydrogen, b) carbon, hydrogen and oxygen, c) carbon, hydrogen, oxygen and nitrogen, or d) carbon, hydrogen and nitrogen.

4. Plasma deposition of the moisture barrier layer is C α H β The method according to claim 1, comprising plasma excitation of a hydrocarbon precursor having the formula (wherein α is an integer of 1 or more, and β is an integer of 1 or more).

5. The hydrocarbon precursor includes CH ３ , C ２ H ２ , C ２ H ４ , C ３ H ７ , or C ６ H ５ CH=CH ２ The method according to claim 4, wherein the method includes the above components.

6. Plasma deposition of the moisture barrier layer is C α H β O γ The method according to claim 1, comprising plasma excitation of an aldehyde precursor having the formula (wherein α is an integer of 1 or more, β is an integer of 1 or more, and γ is an integer of 1 or more).

7. Plasma deposition of the moisture barrier layer is C α H β N γ O δ The method according to claim 1, comprising plasma excitation of an amine precursor having the formula (wherein α is an integer of 1 or more, β is an integer of 1 or more, γ is an integer of 1 or more, and δ is an integer of 0 or more).

8. The method according to claim 1, wherein the deposition of the moisture barrier layer in the plasma is carried out in a capacitively coupled plasma (CCP) processing chamber having a source frequency of 13.56 MHz to 60 MHz, a source power of about 10 W to about 500 W, an ion energy of about 50 eV or less, a gas pressure of about 100 mTorr to about 20 Torr, and a substrate temperature of less than about 100°C.

9. The method according to claim 1, wherein the EUV-activated photoresist film comprises an organometallic oxide containing tin (Sn), zirconium (Zr), indium (In), antimony (Sb), bismuth (Bi), hafnium (Hf), or aluminum (Al).

10. The moisture barrier layer is permeable to EUV rays, and the patterning of the EUV-activated photoresist film is The moisture barrier layer and the EUV-activated photoresist film are exposed to EUV rays, wherein the reaction regions of the EUV-activated photoresist film exposed to the EUV rays are converted into reacted photoresist, and the unreacted regions of the EUV-activated photoresist film that were not exposed to the EUV rays remain unreacted. Removing the aforementioned moisture barrier layer, The method according to claim 1, comprising: removing the unreacted region of the EUV-activated photoresist film to form a first photoresist pattern; or removing the reacted region of the EUV-activated photoresist film to form a second photoresist pattern on the semiconductor substrate.

11. The method according to claim 10, further comprising selectively depositing a material film on the upper surface of the first photoresist pattern with respect to the exposed surface of the semiconductor substrate.

12. The method according to claim 10, further comprising selectively depositing a material film on the exposed surface of the semiconductor substrate relative to the second photoresist pattern.

13. The moisture barrier layer is reactive to EUV rays, and the patterning of the EUV-activated photoresist film is The moisture barrier layer is exposed to EUV rays, wherein a first region of the moisture barrier layer exposed to the EUV rays is converted into a reacted moisture barrier layer, and a second region of the moisture barrier layer not exposed to the EUV rays remains unreacted. The first region of the moisture barrier layer that has been converted into the reacted moisture barrier layer is removed to form a patterned moisture barrier layer, The method according to claim 1, comprising exposing the EUV-activated photoresist film to EUV rays through openings in the patterned moisture barrier layer, wherein the reaction regions of the EUV-activated photoresist film exposed to the EUV rays are converted into reacted photoresist, and the unreacted regions of the EUV-activated photoresist film that were not exposed to the EUV rays remain unreacted.

14. The method according to claim 13, further comprising selectively depositing a material film on the upper surface of the reacted photoresist.

15. The method according to claim 13, further comprising removing the patterned moisture barrier layer.

16. A method for processing a semiconductor substrate, wherein the method is Plasma deposition of a first hydrocarbon polymer layer onto the surface of the semiconductor substrate, The method involves forming an extreme ultraviolet (EUV) active photoresist film on the first hydrocarbon polymer layer using chemical vapor deposition (CVP), wherein the EUV active photoresist film is an organometallic oxide polymer film having carbon-carbon bonds. Plasma deposition of a second hydrocarbon polymer layer onto the EUV-activated photoresist film, wherein the second hydrocarbon polymer layer is either permeable to EUV rays or reactive to EUV rays during plasma deposition. A method comprising patterning the EUV-activated photoresist film using EUV lithography to form a patterned photoresist on the surface of the semiconductor substrate.

17. The method according to claim 16, wherein forming the EUV-activated photoresist film comprises depositing a non-solid organometallic oxide polymer layer on the first hydrocarbon polymer layer using CVP, and further polymerizing the non-solid organometallic oxide polymer layer by heat treatment of the semiconductor substrate to form the EUV-activated photoresist film.

18. The method according to claim 16, wherein the first hydrocarbon polymer layer and the second hydrocarbon polymer layer each comprise a) carbon and hydrogen, b) carbon, hydrogen and oxygen, c) carbon, hydrogen, oxygen and nitrogen, or d) carbon, hydrogen and nitrogen.

19. At least one of the following is to deposit the first hydrocarbon polymer layer using the plasma and to deposit the second hydrocarbon polymer layer using the plasma: α H β The method according to claim 16, comprising plasma excitation of a hydrocarbon precursor having the formula (wherein α is an integer of 1 or more, and β is an integer of 1 or more).

20. The hydrocarbon precursor is CH ３ , C ２ H ２ , C ２ H ４ , C ３ H ７ , or C ６ H ５ CH=CH ２ The method according to claim 19, including the method described in claim 19.

21. At least one of the following is to deposit the first hydrocarbon polymer layer using the plasma and to deposit the second hydrocarbon polymer layer using the plasma: α H β O γ The method according to claim 16, comprising plasma excitation of an aldehyde precursor having the formula (wherein α is an integer of 1 or more, β is an integer of 1 or more, and γ is an integer of 1 or more).

22. At least one of the following is to deposit the first hydrocarbon polymer layer using the plasma and to deposit the second hydrocarbon polymer layer using the plasma: α H β N γ O δ The method according to claim 16, comprising plasma excitation of an amine precursor having the formula (wherein α is an integer of 1 or more, β is an integer of 1 or more, γ is an integer of 1 or more, and δ is an integer of 0 or more).

23. The method according to claim 16, wherein the EUV-activated photoresist film comprises an organometallic oxide containing tin (Sn), zirconium (Zr), indium (In), antimony (Sb), bismuth (Bi), hafnium (Hf), or aluminum (Al).

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