Alumina-carbon hybrid hard mask and method for fabricating the same

Abstract

Embodiments of the present disclosure generally relate to methods for etching a carbon hard mask to have improved etching selectivity and profile control. In some embodiments, a method is provided for processing a carbon hard mask layer, which includes positioning a workpiece within a process area of ​​a processing chamber, wherein the workpiece has a carbon hard mask layer positioned on or throughout the underlying layer, and processing the carbon hard mask layer by exposing the workpiece to a sequential penetration synthesis (SIS) process to produce an alumina-carbon hybrid hard mask denser than the carbon hard mask layer. The SIS process includes exposing the carbon hard mask layer to an aluminum precursor to penetrate the carbon hard mask layer with the aluminum precursor, purging and removing gaseous residues, exposing the carbon hard mask layer to an oxidizing agent to penetrate the carbon hard mask layer with the oxidizing agent to produce an alumina coating positioned on the inner surface of the carbon hard mask layer, and purging the process area to remove gaseous residues.

Description

Technical Field

[0001] Cross - reference to Related Art

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 419,589, filed on October 26, 2022, which is hereby incorporated by reference in its entirety.

[0002] Field

[0002] Embodiments of the present disclosure generally relate to photoresist technology, and more particularly, to methods for enhancing photoresists to improve etching selectivity and profile control.

Background Art

[0003]

[0003] Integrated circuits have evolved into complex devices that can include millions of components (e.g., transistors, capacitors, and resistors) on a single chip. Photolithography can be used to form components on the chip. Generally, the process of photolithography involves forming a photoresist layer on a substrate. This photoresist layer can be formed, for example, by spin - coating. The photoresist layer may include a resist resin and a photoacid generator. The photoacid generator changes the solubility of the photoresist in the development process when exposed to electromagnetic radiation in a subsequent exposure step. The electromagnetic radiation can have any suitable wavelength, such as a wavelength in the extreme ultraviolet region, and can be from any suitable source, such as an ArF laser at 193 nm, an electron beam, an ion beam, or from other sources. Then, in a pre - exposure bake process, excess solvent can be removed.

[0004]

[0004] During the exposure stage, a photomask or reticle may be used to selectively expose a specific area of ​​the photoresist layer placed on the substrate to electromagnetic radiation. Other exposure methods may be maskless exposure methods. Exposure decomposes the photoacid generator, thereby generating acid and creating a latent image of acid within the resist resin. After exposure, the substrate may be heated in a post-exposure bake process. During the post-exposure bake process, the acid generated by the photoacid generator reacts with the resist resin in the photoresist layer, changing the solubility of the resist in the photoresist layer during the subsequent development process.

[0005]

[0005] After exposure and baking, the substrate and photoresist layer are developed and rinsed. Subsequently, a patterned photoresist layer is formed on the substrate. Openings are defined within the patterned photoresist layer, and after the development and rinsing processes, the underlying target material is exposed and etched to transfer the features onto the target material. Factors such as inaccurate control of the lithography exposure process, low resolution, or the resilience of the patterned layer can worsen the critical dimensions of the patterned photoresist layer, resulting in unacceptable line width roughness (LWR). High line width roughness (LWR) of the patterned photoresist layer can lead to inaccurate feature transfer to the target material, ultimately resulting in premature device failure and yield loss.

[0006]

[0006] Carbon-based hard masks are a type of specialized photoresist material used in the industry. However, existing carbon-based hard mask materials have limited etching selectivity between the PR layer and its underlying layers. Carbon-based hard masks have limited etching resistance and often degrade slightly or lose functionality during the etching process. Furthermore, existing carbon-based hard mask materials have drawbacks such as defects in pattern transfer and unsatisfactory line edge roughness (LER) and line width roughness (LWR).

[0007]

[0007] Therefore, there is a need for improved carbon-based hard masks that overcome these disadvantages and for methods for preparing such carbon-based hard masks. [Overview of the Initiative]

[0008]

[0008] Embodiments of the present disclosure generally relate to hard masks having improved etching selectivity and profile control, and methods for preparing such hard masks. The hard mask is an alumina-carbon hybrid hard mask that can be prepared from a carbon hard mask. For example, an alumina-carbon hybrid hard mask can be produced or generated by processing a carbon hard mask layer by a sequential infiltration synthesis (SIS) process.

[0009]

[0009] In one or more embodiments, a method for processing a carbon hard mask layer is provided, which includes positioning a workpiece inside a process area of ​​a processing chamber, wherein the workpiece has a carbon hard mask layer disposed on or throughout the underlying layer, and processing the carbon hard mask layer by exposing the workpiece to an SIS process to produce an alumina-carbon hybrid hard mask denser than the carbon hard mask layer. The SIS process includes one or more infiltration cycles, each of which includes exposing the carbon hard mask layer to an aluminum precursor, infiltrating the carbon hard mask layer with the aluminum precursor through pores contained in the carbon hard mask layer, purging the process area to remove gaseous residue containing the aluminum precursor, exposing the carbon hard mask layer to an oxidizing agent, infiltrating the carbon hard mask layer with the oxidizing agent through pores contained in the carbon hard mask layer to produce an alumina coating disposed on the inner surface of the carbon hard mask layer, and purging the process area to remove gaseous residue containing the oxidizing agent.

[0010]

[0010] In other embodiments, a method is provided for forming a device, which includes positioning a workpiece inside a process area of ​​a processing chamber, the workpiece including a carbon hard mask layer disposed on or over the underlying layer, a silicon-containing hard mask disposed on or over the carbon hard mask layer, and a patterned photoresist layer having a feature pattern disposed on the silicon-containing hard mask. The method also includes etching the silicon-containing hard mask and the carbon hard mask layer so that each has a feature pattern of the patterned photoresist layer, processing the carbon hard mask layer by exposing the workpiece to an SIS process to produce an alumina-carbon hybrid hard mask denser than the carbon hard mask layer, and then etching the underlying layer to have a feature pattern of the patterned photoresist layer.

[0011]

[0011] In some embodiments, a method is provided for forming a device, which includes positioning a workpiece inside a process area of ​​a processing chamber, the workpiece including a metal or metal nitride layer disposed on or over the substrate, a silicon-containing hard mask disposed on or over the metal or metal nitride layer, and a patterned photoresist layer having a feature pattern disposed on the silicon-containing hard mask. The method further includes etching the silicon-containing hard mask to have a feature pattern in the patterned photoresist layer, removing the patterned photoresist layer from the silicon-containing hard mask, and depositing a carbon hard mask layer at least within the feature pattern of the patterned photoresist layer. The method also includes treating the carbon hard mask layer by exposing the workpiece to an SIS process to produce an alumina-carbon hybrid hard mask with a density greater than that of the carbon hard mask layer, and then etching the silicon-containing hard mask to produce an inverted pattern inside the alumina-carbon hybrid hard mask.

[0012]

[0012] In other embodiments, a method is provided for forming a device, which includes positioning a workpiece inside a process area of ​​a processing chamber, the workpiece including a metal or metal nitride layer disposed on or over the substrate, a silicon-containing hard mask disposed on or over the metal or metal nitride layer, and a patterned photoresist layer having a feature pattern disposed on the silicon-containing hard mask. The method also includes etching the silicon-containing hard mask to have a feature pattern in the patterned photoresist layer, removing the patterned photoresist layer from the silicon-containing hard mask, and depositing a carbon hard mask layer within the feature pattern of the patterned photoresist layer and on the top surface of the patterned photoresist layer. The method further includes depositing a photoresist-anti-reflective coating (PR-ARC) layer on a first portion of the carbon hard mask layer, leaving a second portion of the carbon hard mask layer exposed. The method also includes etching a second portion of the carbon hard mask layer while maintaining a first portion of the PR-ARC layer and the carbon hard mask layer on the workpiece during a first mask etching process, and etching the PR-ARC layer while maintaining a first portion of the carbon hard mask layer on the workpiece during a second mask etching process. The method further includes treating a first portion of the carbon hard mask layer by exposing the workpiece to an SIS process to produce an alumina-carbon hybrid hard mask with a density higher than that of the carbon hard mask layer. [Brief explanation of the drawing]

[0013]

[0013] To enable a more detailed understanding of the features of the present disclosure, which have been briefly summarized above, a more detailed description of the present disclosure can be obtained by reference to embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the accompanying drawings only illustrate exemplary embodiments and should not be considered limiting in scope, as other equally valid embodiments are also permissible.

[0014] [Figure 1]

[0014] 1A to 1C are cross-sectional views of a workpiece at different stages of a processing process as described and explained in one or more embodiments of this specification. [Figure 2]

[0015] 2A to 2D are cross-sectional views of another workpiece at different stages of a process for preparing or forming a device, as described and explained in one or more embodiments herein. [Figure 3A-C]

[0016] 3A to 3C are cross-sectional views of another workpiece at different stages of a process for preparing or forming a device, as described and explained in one or more embodiments herein. [Figure 3D-F] 3D to 3F are cross-sectional views of another workpiece at different stages of the process for preparing or forming a device, as described and explained in one or more embodiments herein. [Figure 4A-D]

[0017] 4A to 4D are cross-sectional views of another workpiece at different stages of a process for preparing or forming a device, as described and explained in one or more embodiments herein. [Figure 4E-G] 4E-4G are cross-sectional views of another workpiece at different stages of a process for preparing or forming a device, as described and explained in one or more embodiments herein.

[0015]

[0018] For ease of understanding, the same reference numerals have been used to indicate identical elements common to the drawings, where possible. It is assumed that elements and features of one or more embodiments may be usefully incorporated into other embodiments. [Modes for carrying out the invention]

[0016]

[0019] Embodiments of this disclosure generally relate to hard masks having improved etching selectivity and profile control, and methods for preparing such hard masks. The hard mask is an alumina-carbon hybrid hard mask that can be prepared from a carbon hard mask. In one or more embodiments, a carbon hard mask layer is processed by a sequential infiltration synthesis (SIS) process to produce or generate an alumina-carbon hybrid hard mask. The alumina-carbon hybrid hard mask is denser than the carbon hard mask layer used to form the alumina-carbon hybrid hard mask. The alumina-carbon hybrid hard mask can be used during the fabrication, manufacture, or preparation of various devices, such as memory devices, logic devices, various microelectronic devices, and other types of devices. A wide variety of workpieces or devices containing alumina-carbon hybrid hard masks can be prepared, manufactured, processed, or fabricated by the methods described herein.

[0017]

[0020] Figures 1A-1C are cross-sectional views of a workpiece 100 at different stages of a processing process, such as an SIS process, as described and explained in one or more embodiments herein. The SIS process is used to produce a processed mask or patterned photoresist (PR) layer that is denser and harder than the unprocessed or original mask or patterned PR layer. In one or more embodiments, a method 110 for processing a carbon hard mask layer is provided, which includes positioning the workpiece 100 inside a process area of ​​a processing chamber. The workpiece 100 has a carbon hard mask layer 110 placed on or across an underlying layer 104, as shown in Figure 1A. As shown, the underlying layer 104 can be formed, deposited, or otherwise placed on any other layer (not shown) or substrate 102. The method includes processing the carbon hard mask layer 110 by exposing the workpiece 100 to the SIS process to produce an intermediate mask 118 shown in Figure 1B, and then producing an alumina-carbon hybrid hard mask 120 shown in Figure 1C. The alumina-carbon hybrid hard mask 120 has a higher density than the carbon hard mask layer 110.

[0018]

[0021] In one or more embodiments, the SIS process comprises one or more penetration cycles, each of which comprises successively exposing the carbon hard mask layer 110 to an aluminum precursor, allowing the aluminum precursor to penetrate the carbon hard mask layer 110 through pores contained within the carbon hard mask layer 110, and purging the process area to remove the gaseous residue of the aluminum precursor. At this stage, the carbon hard mask layer 110 begins to be converted into an intermediate mask 118 in which aluminum is incorporated inside and on the inner surface of the carbon hard mask layer 110. The SIS process further comprises successively exposing the carbon hard mask layer 110 to an oxidizing agent, allowing the oxidizing agent to penetrate the carbon hard mask layer 110 through pores contained within the carbon hard mask layer 110 to produce an alumina coating disposed on the inner surface of the carbon hard mask layer 110, and purging the process area to remove the gaseous residue containing the oxidizing agent. In some embodiments, the processing process comprises only one penetration cycle that processes the carbon hard mask layer 110. In other embodiments, the penetration cycle can be repeated many times (e.g., from 2 to about 100 times, or more) to treat the carbon hard mask layer 110.

[0019]

[0022] The substrate 102 may be made of one or more materials, depending on the application, such as silicon, silicon oxide, doped silicon, silicon germanium, germanium, gallium arsenide, glass, sapphire, and any other material, such as metals, metal nitrides, metal alloys, and other conductive or semiconducting materials, or may include them. The substrate 102, or its surface, may also be made of dielectric materials, such as silicon dioxide, silicon nitride, organic silicates, and carbon-doped silicon oxide or nitride materials. The substrate 102 can be any shape and dimension, such as circular, square, or rectangular. In some embodiments, the substrate 102 is circular and has a diameter of 200 mm, 250 mm, 300 mm, or 450 mm.

[0020]

[0023] The lower layer 104 can be or can include an oxide layer or a silicon-containing layer, such as silicon oxide, amorphous silicon, tetraethoxysilane (TEOS) layer, or a combination thereof. The lower layer 104 can be formed or produced by chemical vapor deposition (CVD) or plasma-enhanced CVD (PECVD). In one or more embodiments, the lower layer 104 can be or can include a metal oxide, a metal nitride, silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof. In some embodiments, the lower layer 104 can be or can include a stack disposed on or over the substrate 102. In one or more examples, the stack includes alternating layers of a silicon oxide layer and a silicon nitride layer.

[0021]

[0024] In one or more embodiments, the carbon hard mask layer 110 can be or can include carbon, amorphous carbon, spin-on carbon (SOC), dopants thereof, or any combination thereof. The carbon hard mask layer 110 can be formed, deposited, or produced by one or more processes, such as a thermal chemical vapor deposition (CVD) process, a plasma-enhanced CVD (PE-CVD) process, a fluidized CVD (FCVD) process, or a spin-on process. The carbon hard mask layer 110 can be or can include a mask or other patterned layer generated, prepared, or produced by one or more processes. In some examples, the carbon hard mask layer 110 is prepared by a lithography process, such as an extreme ultraviolet (EUV) lithography process. The carbon hard mask layer 110 is porous and can have pores throughout the material including all surfaces of the carbon hard mask layer 110. In FIG. 1A, the carbon hard mask layer 110 is formed but remains untreated with respect to the SIS process described and explained herein.

[0022]

[0025] In one or more embodiments, the carbon hard mask layer 110 has a thickness in the range of from about 1 μm to about 20 μm, from about 2 μm to about 10 μm, or from about 3 μm to about 6 μm. The carbon hard mask layer 110 can be or can include a patterned layer that includes the feature pattern of the features 112 shown in FIGS. 1A - C. The features 112 can have a height that is less than or equal to the thickness of the carbon hard mask layer 110. Thus, the features 112 can have a height in the range of from about 1 μm to about 20 μm, from about 2 μm to about 10 μm, or from about 3 μm to about 6 μm. The features 112 of the patterned layer or the carbon hard mask layer 110 are separated by vias, gaps, or spaces that can have a width in the range of from about 5 nm to about 250 nm, from about 10 nm to about 150 nm, or from about 20 nm to about 100 nm. The features 112 can have an aspect ratio in the range of from about 20 to about 500, from about 30 to about 300, or from about 40 to about 200.

[0023] <着

[0026] In one or more embodiments, the carbon hard mask layer 110 can be or can include a carbon-containing material having polar functional groups, such as one or more C-H groups, one or more C-O groups, one or more C=O groups, or any combination thereof. During the SIS process, the polar functional groups on the inner surface of the carbon hard mask layer 110 assist in the formation and / or deposition of the alumina coating via the intermediate mask 118.

[0024]

[0027] In some embodiments, the carbon hard mask layer 110 may contain carbon ranging from about 30 atomic percent (at%), about 40 at%, or about 50 at%, to about 60 at%, about 70 at%, or about 80 at%. For example, the carbon hard mask layer 110 may contain carbon ranging from about 30 at% to about 80 at%, about 40 at% to about 80 at%, about 50 at% to about 80 at%, about 60 at% to about 80 at%, about 70 at% to about 80 at%, about 30 at% to about 65 at%, about 40 at% to about 65 at%, about 50 at% to about 65 at%, about 60 at% to about 65 at%, about 30 at% to about 50 at%, about 40 at% to about 50 at%, or about 45 at% to about 50 at%.

[0025]

[0028] The carbon hard mask layer 110 can contain hydrogen in the range of approximately 10 at%, 15 at%, 20 at%, or 25 at%, to approximately 30 at%, 35 at%, 40 at%, 45 at%, or 50 at%. For example, the carbon hard mask layer 110 may contain hydrogen in the range of approximately 10 at% to 50 at%, approximately 15 at% to 50 at%, approximately 20 at% to 50 at%, approximately 25 at% to 50 at%, approximately 30 at% to 50 at%, approximately 40 at% to 50 at%, approximately 10 at% to 40 at%, approximately 15 at% to 40 at%, approximately 20 at% to 40 at%, approximately 25 at% to 40 at%, approximately 30 at% to 40 at%, approximately 35 at% to 40 at%, approximately 10 at% to 30 at%, approximately 15 at% to 30 at%, approximately 20 at% to 30 at%, or approximately 25 at% to 30 at%.

[0026]

[0029] The carbon hard mask layer 110 can contain oxygen in the range of approximately 1 at%, 2 at%, 3 at%, 3 at%, 5 at%, 6 at%, 8 at%, or 10 at%, to approximately 12 at%, 15 at%, 16 at%, 18 at%, or 20 at%. For example, the carbon hard mask layer 110 may contain oxygen in the range of approximately 1 at% to 20 at%, approximately 2 at% to 20 at%, approximately 5 at% to 20 at%, approximately 8 at% to 20 at%, approximately 10 at% to 20 at%, approximately 12 at% to 20 at%, approximately 15 at% to 20 at%, approximately 18 at% to 20 at%, approximately 1 at% to 15 at%, approximately 2 at% to 15 at%, approximately 5 at% to 15 at%, approximately 8 at% to 15 at%, approximately 10 at% to 15 at%, approximately 12 at% to 15 at%, approximately 15 at% to 15 at%, approximately 18 at% to 15 at%, approximately 1 at% to 10 at%, approximately 2 at% to 10 at%, approximately 5 at% to 10 at%, or approximately 8 at% to 10 at%.

[0027]

[0030] In one or more embodiments, the carbon hard mask layer 110 may contain about 30 at% to about 80 at% carbon, about 10 at% to about 50 at% hydrogen, and about 10 at% to about 20 at% oxygen. In some embodiments, the carbon hard mask layer 110 may contain about 40 at% to about 60 at% carbon, about 20 at% to about 40 at% hydrogen, and about 12 at% to about 18 at% oxygen. In other embodiments, the carbon hard mask layer 110 may contain about 45 at% to about 55 at% carbon, about 25 at% to about 35 at% hydrogen, and about 14 at% to about 16 at% oxygen.

[0028]

[0031] Figure 1B shows a workpiece 100 having an intermediate mask 118, the intermediate mask having an aluminum precursor or other metal precursor absorbed or otherwise incorporated within and on the inner surface of a carbon hard mask layer 110. The coating that penetrates the precursor coats the entire inner surface of the carbon hard mask layer 110 or is otherwise distributed across the entire inner surface. The aluminum or other metal precursor penetrates the pores contained throughout the carbon hard mask layer 110. The penetrating coating contains an absorbed and / or condensed amount of precursor, for example, during the first process segment of the SIS process. Subsequently, during the second process segment of the SIS process, the process area of ​​the processing chamber can be purged to remove any excess or remaining precursor inside the process area.

[0029]

[0032] Figure 1C shows a workpiece 100 having an alumina-carbon hybrid hard mask 120, which includes an alumina (or other metal oxide) coating formed inside and on the carbon hard mask layer 110. During the third process segment of the SIS process, the penetrating coating is oxidized by exposure to an oxidizing agent to form an oxide coating of the alumina-carbon hybrid hard mask 120. Subsequently, during the fourth process segment of the SIS process, the process area of ​​the processing chamber can be purged to remove any excess or remaining precursor inside the process area. The alumina-carbon hybrid hard mask 120, including the alumina coating shown in Figure 1C, has higher density and hardness than the carbon hard mask layer 110 shown in Figure 1A.

[0030]

[0033] The alumina-carbon hybrid hard mask 120 contains at least aluminum, oxygen, and carbon. In one or more embodiments, the alumina-carbon hybrid hard mask 120 may contain aluminum ranging from about 3 at%, about 4 at%, about 5 at%, about 6 at%, about 8 at%, or about 10 at%, to about 12 at%, about 14 at%, about 15 at%, about 16 at%, about 18 at%, about 20 at%, about 22 at%, or about 25 at%. For example, the alumina-carbon hybrid hard mask 120 may contain aluminum in the range of approximately 3 at% to 25 at%, approximately 3 at% to 20 at%, approximately 5 at% to 20 at%, approximately 8 at% to 20 at%, approximately 10 at% to 20 at%, approximately 12 at% to 20 at%, approximately 15 at% to 20 at%, approximately 18 at% to 20 at%, approximately 3 at% to 15 at%, approximately 5 at% to 15 at%, approximately 8 at% to 15 at%, approximately 10 at% to 15 at%, approximately 12 at% to 15 at%, approximately 14 at% to 15 at%, approximately 3 at% to 10 at%, approximately 5 at% to 10 at%, or approximately 8 at% to 10 at%.

[0031]

[0034] The alumina-carbon hybrid hard mask 120 can contain oxygen ranging from approximately 3 at%, 4 at%, 5 at%, 6 at%, 8 at%, or 10 at%, to approximately 12 at%, 15 at%, 18 at%, 20 at%, 22 at%, 25 at%, 28 at%, 30 at%, or 35 at%. For example, the alumina-carbon hybrid hard mask 120 is suitable for approximately 3 at% to 35 at%, approximately 3 at% to 30 at%, approximately 3 at% to 25 at%, approximately 3 at% to 20 at%, approximately 5 at% to 35 at%, approximately 5 at% to 30 at%, approximately 5 at% to 25 at%, approximately 5 at% to 20 at%, approximately 8 at% to 20 at%, approximately 10 at% to 20 at%, approximately 12 at% to 20 at%, approximately 15 at% to 20 at%, approximately 18 at% to 20 at%, and approximately 5 at% to 3 It can contain oxygen in the range of 0 at%, approximately 8 at% to 30 at%, approximately 10 at% to 30 at%, approximately 12 at% to 30 at%, approximately 15 at% to 30 at%, approximately 18 at% to 30 at%, approximately 3 at% to 15 at%, approximately 5 at% to 15 at%, approximately 8 at% to 15 at%, approximately 10 at% to 15 at%, approximately 12 at% to 15 at%, approximately 14 at% to 15 at%, approximately 3 at% to 10 at%, approximately 5 at% to 10 at%, or approximately 8 at% to 10 at%.

[0032]

[0035] Alumina-carbon hybrid hard mask 120 can contain carbon ranging from approximately 40 at%, 45 at%, 50 at%, 55 at%, 60 at%, or 65 at%, to approximately 70 at%, 75 at%, 80 at%, 85 at%, 90 at%, or 95 at%. For example, the alumina-carbon hybrid hard mask 120 may contain carbon in the range of approximately 40 at% to 90 at%, 50 at% to 90 at%, 60 at% to 90 at%, 70 at% to 90 at%, 80 at% to 90 at%, 40 at% to 75 at%, 50 at% to 75 at%, 60 at% to 75 at%, 70 at% to 75 at%, 40 at% to 60 at%, 45 at% to 60 at%, 50 at% to 60 at%, or 55 at% to 60 at%.

[0033]

[0036] In one or more embodiments, the alumina-carbon hybrid hard mask 120 may contain about 5 at% to about 20 at% aluminum, about 5 at% to about 30 at% oxygen, and about 50 at% to about 90 at% carbon. In some embodiments, the alumina-carbon hybrid hard mask 120 may contain about 10 at% to about 20 at% aluminum, about 10 at% to about 30 at% oxygen, and about 50 at% to about 80 at% carbon. In one or more embodiments, the alumina-carbon hybrid hard mask 120 may contain about 5 at% to about 10 at% aluminum, about 5 at% to about 20 at% oxygen, and about 70 at% to about 90 at% carbon.

[0034]

[0037] The alumina-carbon hybrid hard mask 120 has a thickness in the range of approximately 1 μm to approximately 20 μm, approximately 2 μm to approximately 10 μm, or approximately 3 μm to approximately 6 μm. The alumina-carbon hybrid hard mask 120 may be a patterned layer containing the feature pattern of feature 112 shown in Figure 1C, or may include such a layer. Feature 112 may have a height less than or equal to the thickness of the alumina-carbon hybrid hard mask 120. Therefore, feature 112 may have a height in the range of approximately 1 μm to approximately 20 μm, approximately 2 μm to approximately 10 μm, or approximately 3 μm to approximately 6 μm. The patterned layer or feature 112 of the alumina-carbon hybrid hard mask 120 is separated by vias, gaps, or spaces which may have a width of approximately 5 nm to approximately 250 nm, approximately 10 nm to approximately 150 nm, or approximately 20 nm to approximately 100 nm. Feature 112 can have an aspect ratio of approximately 20 to 500, approximately 30 to 300, or approximately 40 to 200.

[0035] Sequential Infiltration Synthesis (SIS) Process

[0038] The SIS process described herein for preparing an alumina-carbon hybrid hard mask 120 from a carbon hard mask layer 110, as shown in Figures 1A-C, can also be used to convert any carbon hard mask layer into an alumina-carbon hybrid hard mask, such as those shown in Figures 2A-4G.

[0036]

[0039] In one or more embodiments, the SIS process includes one or more penetration cycles of exposing the carbon hard mask layer 110 to an aluminum-containing precursor (e.g., one or more aluminum precursors), impregnating the carbon hard mask layer 110 with the precursor through pores contained in the carbon hard mask layer 110, purging the process area to remove gaseous residue containing the precursor, exposing the carbon hard mask layer 110 to an oxidizing agent, impregnating the carbon hard mask layer 110 with the oxidizing agent through pores contained in the carbon hard mask layer 110 to produce an alumina coating disposed on the inner surface of the carbon hard mask layer 110, and purging the process area to remove gaseous residue containing the oxidizing agent.

[0037]

[0040] Each infiltration cycle of the SIS process includes a first process segment for exposure and infiltration with a precursor, a second process segment for purging the process area to remove remaining gaseous precursors, a third process segment for exposure and infiltration with an oxidizer, and a fourth process segment for purging the process area to remove remaining gaseous precursors. The process segments of the infiltration cycle are repeated consecutively between each infiltration cycle. One or more carrier gases can be introduced into the process area along the precursor and / or oxidizer between the first and third process segments of the SIS process. One or more purge gases can be introduced into the process area, and the process area is emptied between the second and fourth process segments of the SIS process. The carrier gases and purge gases may have the same or different compositions. Exemplary carrier gases and / or purge gases may be argon, helium, neon, nitrogen (N2), hydrogen (H2), or any combination thereof, or may include them.

[0038]

[0041] The process area of ​​the processing chamber is the internal space inside the processing chamber. The process area and / or internal space of the processing chamber are maintained and / or regulated to one or more pressures below atmospheric pressure or ambient pressure (e.g., less than 760 Torr) during the SIS process. The pressure of the process area and / or internal space of the processing chamber during the SIS process ranges from approximately 0.01 Torr, approximately 0.1 Torr, approximately 1 Torr, approximately 1 Torr, approximately 5 Torr, approximately 10 Torr, approximately 15 Torr, approximately 20 Torr, approximately 25 Torr, approximately 35 Torr, or approximately 50 Torr, to approximately 80 Torr, approximately 100 Torr, approximately 150 Torr, approximately 200 Torr, approximately 250 Torr, approximately 300 Torr, approximately 350 Torr, approximately 400 Torr, approximately 450 Torr, approximately 500 Torr, or approximately 600 Torr. For example, the pressure in the process area and / or internal space of the processing chamber during the SIS process is approximately 0.01 Torre to approximately 600 Torre, approximately 0.01 Torre to approximately 500 Torre, approximately 0.01 Torre to approximately 400 Torre, approximately 0.01 Torre to approximately 350 Torre, approximately 0.01 Torre to approximately 300 Torre, approximately 0.01 Torre to approximately 250 Torre, approximately 0.01 Torre to approximately 200 Torre, approximately 0.01 Torre to approximately 150 Torre, and approximately 0 From 0.01 to approximately 100 toll, from approximately 0.01 to approximately 50 toll, from approximately 0.1 to approximately 600 toll, from approximately 0.1 to approximately 500 toll, from approximately 0.1 to approximately 400 toll, from approximately 0.1 to approximately 350 toll, from approximately 0.1 to approximately 300 toll, from approximately 0.1 to approximately 250 toll, from approximately 0.1 to approximately 200 toll, from approximately 0.1 to approximately 150 toll, from approximately 0.1 to approximately 100 toll, and approximately 0.1 to approximately 50 tolls, approximately 1 to approximately 600 tolls, approximately 1 to approximately 500 tolls, approximately 1 to approximately 400 tolls, approximately 1 to approximately 350 tolls, approximately 1 to approximately 300 tolls, approximately 1 to approximately 250 tolls, approximately 1 to approximately 200 tolls, approximately 1 to approximately 150 tolls, approximately 1 to approximately 100 tolls, approximately 1 to approximately 50 tolls, approximately 10 to approximately 600 tolls, approximately 10 to approximately 500 tolls , approximately 10 to 400 to 1 , approximately 15 to 300 to , approximately 15 to 250 to , approximately 15 to 200 to , approximately 15 to 150 to , approximately 15 to 100 to , approximately 15 to 50 to , approximately 50 to 600 to , approximately 50 to 500 to , approximately 50 to 400 to , approximately 50 to 350 to , approximately 50 to 300 to , approximately 50 to 250 to The pressures are approximately 50 Tor to 200 Tor, 50 Tor to 150 Tor, 50 Tor to 100 Tor, 100 Tor to 600 Tor, 100 Tor to 500 Tor, 100 Tor to 400 Tor, 100 Tor to 350 Tor, 100 Tor to 300 Tor, 100 Tor to 250 Tor, 100 Tor to 200 Tor, or 100 Tor to 150 Tor. In one or more embodiments, the pressure in the process area and / or internal space of the processing chamber is approximately 0.01 Tor to 250 Tor, or approximately 0.1 Tor to 50 Tor during the SIS process.

[0039]

[0042] During the SIS process, each of the first and third process segments of the penetration cycle can independently last from approximately 20 seconds, 30 seconds, 35 seconds, 40 seconds, or 45 seconds to approximately 50 seconds, 60 seconds, 70 seconds, 80 seconds, 90 seconds, 100 seconds, 2 minutes, 2.5 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 8 minutes, 10 minutes, 12 minutes, 15 minutes, 18 minutes, or 20 minutes. For example, during the SIS process, each of the first and third process segments of the penetration cycle independently takes approximately 20 seconds to 20 minutes, 20 seconds to 15 minutes, 20 seconds to 12 minutes, 20 seconds to 10 minutes, 20 seconds to 8 minutes, 20 seconds to 6 minutes, 20 seconds to 5 minutes, 20 seconds to 4 minutes, 20 seconds to 3 minutes, 20 seconds to 2.5 minutes, 20 seconds to 2 minutes, 20 seconds to 100 seconds, 20 seconds to 90 seconds, 20 seconds to 75 seconds, 20 seconds to 60 seconds, 20 seconds to 45 seconds, 20 seconds to 30 seconds, and 40 seconds to 5 minutes. It can last for minutes, approximately 40 seconds to 4 minutes, approximately 40 seconds to 3 minutes, approximately 40 seconds to 2.5 minutes, approximately 40 seconds to 2 minutes, approximately 40 seconds to 100 seconds, approximately 40 seconds to 90 seconds, approximately 40 seconds to 75 seconds, approximately 40 seconds to 60 seconds, approximately 60 seconds to 20 minutes, approximately 60 seconds to 15 minutes, approximately 60 seconds to 12 minutes, approximately 60 seconds to 10 minutes, approximately 60 seconds to 8 minutes, approximately 60 seconds to 6 minutes, approximately 60 seconds to 5 minutes, approximately 60 seconds to 4 minutes, approximately 60 seconds to 3 minutes, approximately 60 seconds to 2.5 minutes, approximately 60 seconds to 2 minutes, approximately 60 seconds to 100 seconds, approximately 60 seconds to 90 seconds, or approximately 60 seconds to 75 seconds.

[0040]

[0043] In one or more embodiments, during the first process segment of each penetration cycle, the carbon hard mask layer 110 is exposed to an aluminum precursor for about 1 to 10 minutes, during which time the aluminum precursor is allowed to penetrate the carbon hard mask layer 110. In some embodiments, during the third process segment of each penetration cycle, the carbon hard mask layer 110 is exposed to an oxidizing agent for about 1 to 10 minutes, during which time the oxidizing agent is allowed to penetrate the carbon hard mask layer 110.

[0041]

[0044] During the SIS process, each of the second and fourth process segments of the penetration cycle can independently last for approximately 20 seconds, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 60 seconds, 70 seconds, 80 seconds, or 90 seconds, 100 seconds, 2 minutes, 2.5 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 8 minutes, 10 minutes, 12 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes. For example, during the SIS process, each of the second and fourth process segments of the penetration cycle independently takes approximately 20 seconds to 30 minutes, 20 seconds to 25 minutes, 20 seconds to 20 minutes, 20 seconds to 15 minutes, 20 seconds to 12 minutes, 20 seconds to 10 minutes, 20 seconds to 8 minutes, 20 seconds to 6 minutes, 20 seconds to 5 minutes, 20 seconds to 4 minutes, 20 seconds to 3 minutes, 20 seconds to 2.5 minutes, 20 seconds to 2 minutes, 20 seconds to 100 seconds, 20 seconds to 90 seconds, 20 seconds to 75 seconds, 20 seconds to 60 seconds, 20 seconds to 45 seconds, and 20 seconds to 3 minutes. It can last for 0 seconds, approximately 40 seconds to 5 minutes, approximately 40 seconds to 4 minutes, approximately 40 seconds to 3 minutes, approximately 40 seconds to 2.5 minutes, approximately 40 seconds to 2 minutes, approximately 40 seconds to 100 seconds, approximately 40 seconds to 90 seconds, approximately 40 seconds to 75 seconds, approximately 40 seconds to 60 seconds, approximately 60 seconds to 20 minutes, approximately 60 seconds to 15 minutes, approximately 60 seconds to 12 minutes, approximately 60 seconds to 10 minutes, approximately 60 seconds to 8 minutes, approximately 60 seconds to 6 minutes, approximately 60 seconds to 5 minutes, approximately 60 seconds to 4 minutes, approximately 60 seconds to 3 minutes, approximately 60 seconds to 2.5 minutes, approximately 60 seconds to 2 minutes, approximately 60 seconds to 100 seconds, approximately 60 seconds to 90 seconds, or approximately 60 seconds to 75 seconds.

[0042]

[0045] In one or more embodiments, the carbon hard mask layer 110 is exposed to a purge gas for about 1 minute to about 30 minutes during the second process segment of each penetration cycle, while the process area is purged to remove gaseous residues containing the aluminum precursor. In other embodiments, the carbon hard mask layer 110 is exposed to a purge gas for about 1 minute to about 30 minutes during the fourth process segment of each penetration cycle, while the process area is purged to remove gaseous residues containing the oxidizer.

[0043]

[0046] The infiltration cycle can be executed once, twice, or multiple times during the SIS process. The process segments of the infiltration cycle are repeated consecutively between each infiltration cycle. In some embodiments, the infiltration cycle is repeated 2, 3, 4, or 5 times, to 6, 7, 8, 9, about 10, about 12, about 15, about 20, about 30, about 40, about 50, about 60, about 80, about 100, or more times during the SIS process. For example, during the SIS process, the infiltration cycle is repeated 2 to about 100 times, 2 to about 80 times, 2 to about 50 times, 2 to about 20 times, 2 to about 15 times, 2 to about 10 times, 2 to 8 times, or 2 to 5 times. In one or more embodiments, the SIS process includes infiltration cycles of 1 to about 100 cycles, 5 to about 80 cycles, about 10 to about 50 cycles, or about 20 to about 40 cycles.

[0044]

[0047] The precursors exposed to the carbon hard mask layer 110 may be one or more aluminum precursors or other metal precursors. The oxidizing agent may be a compound or reagent that oxidizes the aluminum precursor to produce alumina or oxidizes another metal precursor to produce the respective metal oxide, or may include such a compound or reagent. The oxidizing agent may be water, ozone, oxygen plasma, oxygen radicals, oxygen (O2), hydrogen peroxide, or any combination thereof, or may include such a compound or reagent.

[0045]

[0048] In one or more embodiments, the precursor is one or more aluminum precursors or comprises such precursors, and the oxide coating formed inside the carbon hard mask layer 110 is alumina or comprises alumina. The aluminum precursor may be one or more alkylaluminum compounds, one or more alkoxyaluminum compounds, one or more aluminum halide compounds, aluminum hydride, or any combination thereof, or may include such a precursor. In some embodiments, the aluminum precursor may be trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum, diethylaluminum, dipropylaluminum, dibutylaluminum, composites thereof, or combinations thereof, or may include such a precursor.

[0046]

[0049] In one or more embodiments, the aluminum precursor is one or more alkylaluminum compounds (e.g., trimethylaluminum), or comprises such compounds, and the oxidizing agent is water, or comprises water. In other embodiments, the aluminum precursor is one or more alkoxyaluminum compounds, or comprises such compounds, and the oxidizing agent is ozone or oxygen plasma, or comprises ozone or oxygen plasma.

[0047]

[0050] Figures 2A–2D are cross-sectional views of a workpiece 200 at different stages of a process for preparing or forming a device, as described and explained in one or more embodiments herein. The device may be or may include a memory device, a logic device, a microelectronic device, and / or other devices. In one or more embodiments, a method for forming a device is provided, which includes positioning the workpiece 200 inside a process area of ​​a processing chamber. The workpiece 200 includes a carbon hard mask layer 210 disposed on or over the underlying layer 204, a silicon-containing hard mask 230 disposed on or over the carbon hard mask layer 210, and a patterned photoresist (PR) layer 240 having a feature pattern of features 242 disposed on the silicon-containing hard mask 230. The method also includes etching a silicon-containing hard mask 230 and a carbon hard mask layer 210 so that each has a patterned PR layer 240 feature 242, treating the carbon hard mask layer 210 by exposing the workpiece 200 to an SIS process to produce an alumina-carbon hybrid hard mask 220, and then etching the underlying layer 204 so that it has a patterned PR layer 240 feature 242.

[0048]

[0051] The lower layer 204 may be or may include metal oxides, metal nitrides, silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof. The lower layer 204 may be or may include a stack disposed on or over the substrate 202 or the entire substrate 102. In one or more embodiments, the stack includes alternating layers of silicon oxide and silicon nitride. The substrate 202 may be or may include any type of substrate including the substrate 102 described above. In some embodiments, the lower layer 204 may be or may include any type of layer including the lower layer 104 described above.

[0049]

[0052] As shown in Figure 2A, the patterned PR layer 240 can be deposited, formed, positioned, or otherwise arranged on the silicon-containing hard mask 230. In one or more embodiments, the patterned PR layer 240 can be produced or formed by an extreme ultraviolet (EUV) lithography process or a deep ultraviolet (DUV) lithography process. In one or more embodiments, the patterned PR layer 240 can be an EUV stack containing the PR layer below a bottom ARC (BARC) layer, or include such a stack, to provide a PR / BARC stack. In other embodiments, the patterned PR layer 240 can be a DUV stack containing the PR layer below a BARC layer below a dielectric ARC (DARC) layer, or include such a stack, to provide a PR / BARC / DARC stack.

[0050]

[0053] In some embodiments, as shown in Figure 2B, feature 242 is completely etched over the entire thickness of the silicon-containing hard mask 230. The silicon-containing hard mask 230 may be or may contain silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof. In one or more embodiments, the silicon-containing hard mask 230 may be etched or removed by exposure of the silicon-containing hard mask 230 to one or more carbon fluoride etching solutions and one or more process gases. The carbon fluoride etching solutions may be or may contain tetrafluoromethane, trifluoromethane, difluoromethane, monofluoromethane, octafluorocyclobutane, hexafluoro-1,3-butadiene, or any combination thereof. The process gases may be or may contain argon, helium, nitrogen (N2), oxygen (O2), or any combination thereof.

[0051]

[0054] In some embodiments, feature 242 is etched over at least a portion or the entire thickness of the carbon hard mask layer 210, as shown in Figure 2B. The carbon hard mask layer 210 may be or include any type of carbon hard mask, including the carbon hard mask 110 described above. In one or more embodiments, the carbon hard mask layer 210 may be etched or otherwise removed by exposing the carbon hard mask layer 210 to one or more etching gases and one or more passivation gases. The etching gas may be or include argon, oxygen, or a combination thereof, and the passivation gas may be or include methane, sulfur dioxide, carbonyl sulfide, or any combination thereof.

[0052]

[0055] Figures 2B-2C show the processing or transition of the carbon hard mask layer 210 (Figure 2B) to produce the alumina-carbon hybrid hard mask 220 (Figure 2C) via the SIS process. In the workpiece 200, the SIS process is selective for the carbon hard mask layer 210 and non-reactive or substantially non-reactive for other exposed surfaces and layers, such as the underlayer 204, the silicon-containing hard mask 230, and the patterned PR layer 240. The alumina-carbon hybrid hard mask 220 has a higher density than the carbon hard mask layer 210. The alumina-carbon hybrid hard mask 220 may have the same composition and properties as the alumina-carbon hybrid hard mask 120 described above.

[0053]

[0056] In some embodiments, feature 242 is etched over at least a portion or all of the thickness of the underlying layer 204. As shown in Figure 2D, feature 242 is etched only partially of the thickness of the underlying layer 204. The underlying layer 204 can be partially etched by exposing it to one or more carbon fluoride etchants and one or more process gases. The carbon fluoride etchants may be or may include tetrafluoromethane, trifluoromethane, difluoromethane, monofluoromethane, octafluorocyclobutane, hexafluoro-1,3-butadiene, or any combination thereof. The process gases may be or may include argon, helium, nitrogen (N2), oxygen (O2), or any combination thereof.

[0054]

[0057] The alumina-carbon hybrid hard mask 220 contains at least aluminum, oxygen, and carbon. In one or more embodiments, the alumina-carbon hybrid hard mask 220 may contain aluminum in the range of about 3 at%, about 4 at%, about 5 at%, about 6 at%, about 8 at%, or about 10 at%, to about 12 at%, about 14 at%, about 15 at%, about 16 at%, about 18 at%, about 20 at%, about 22 at%, or about 25 at%. For example, the alumina-carbon hybrid hard mask 220 may contain aluminum in the range of approximately 3 at% to 25 at%, approximately 3 at% to 20 at%, approximately 5 at% to 20 at%, approximately 8 at% to 20 at%, approximately 10 at% to 20 at%, approximately 12 at% to 20 at%, approximately 15 at% to 20 at%, approximately 18 at% to 20 at%, approximately 3 at% to 15 at%, approximately 5 at% to 15 at%, approximately 8 at% to 15 at%, approximately 10 at% to 15 at%, approximately 12 at% to 15 at%, approximately 14 at% to 15 at%, approximately 3 at% to 10 at%, approximately 5 at% to 10 at%, or approximately 8 at% to 10 at%.

[0055]

[0058] The Alumina Carbon Hybrid Hard Mask 220 can contain oxygen ranging from approximately 3 at%, 4 at%, 5 at%, 6 at%, 8 at%, or 10 at%, to approximately 12 at%, 15 at%, 18 at%, 20 at%, 22 at%, 25 at%, 28 at%, 30 at%, or 35 at%. For example, the alumina-carbon hybrid hard mask 220 has a range of approximately 3 at% to 35 at%, 3 at% to 30 at%, 3 at% to 25 at%, 3 at% to 20 at%, 5 at% to 35 at%, 5 at% to 30 at%, 5 at% to 25 at%, 5 at% to 20 at%, 8 at% to 20 at%, 10 at% to 20 at%, 12 at% to 20 at%, 15 at% to 20 at%, 18 at% to 20 at%, and 5 at% to 3 It can contain oxygen in the range of 0 at%, approximately 8 at% to 30 at%, approximately 10 at% to 30 at%, approximately 12 at% to 30 at%, approximately 15 at% to 30 at%, approximately 18 at% to 30 at%, approximately 3 at% to 15 at%, approximately 5 at% to 15 at%, approximately 8 at% to 15 at%, approximately 10 at% to 15 at%, approximately 12 at% to 15 at%, approximately 14 at% to 15 at%, approximately 3 at% to 10 at%, approximately 5 at% to 10 at%, or approximately 8 at% to 10 at%.

[0056]

[0059] Alumina-carbon hybrid hard mask 220 can contain carbon ranging from approximately 40 at%, 45 at%, 50 at%, 55 at%, 60 at%, or 65 at%, to approximately 70 at%, 75 at%, 80 at%, 85 at%, 90 at%, or 95 at%. For example, the alumina-carbon hybrid hard mask 220 may contain carbon in the range of approximately 40 at% to 90 at%, 50 at% to 90 at%, 60 at% to 90 at%, 70 at% to 90 at%, 80 at% to 90 at%, 40 at% to 75 at%, 50 at% to 75 at%, 60 at% to 75 at%, 70 at% to 75 at%, 40 at% to 60 at%, 45 at% to 60 at%, 50 at% to 60 at%, or 55 at% to 60 at%.

[0057]

[0060] In one or more embodiments, the alumina-carbon hybrid hard mask 220 may contain about 5 at% to about 20 at% aluminum, about 5 at% to about 30 at% oxygen, and about 50 at% to about 90 at% carbon. In some embodiments, the alumina-carbon hybrid hard mask 220 may contain about 10 at% to about 20 at% aluminum, about 10 at% to about 30 at% oxygen, and about 50 at% to about 80 at% carbon. In one or more embodiments, the alumina-carbon hybrid hard mask 220 may contain about 5 at% to about 10 at% aluminum, about 5 at% to about 20 at% oxygen, and about 70 at% to about 90 at% carbon.

[0058]

[0061] The alumina-carbon hybrid hard mask 220 has a thickness in the range of approximately 1 μm to approximately 20 μm, approximately 2 μm to approximately 10 μm, or approximately 3 μm to approximately 6 μm. The alumina-carbon hybrid hard mask 220 may be a patterned layer containing the feature pattern of feature 242 shown in Figure 2D, or may include such a layer. The feature pattern or feature 242 may have a height less than or equal to the thickness of the alumina-carbon hybrid hard mask 220. Therefore, the feature pattern or feature 242 may have a height in the range of approximately 1 μm to approximately 20 μm, approximately 2 μm to approximately 10 μm, or approximately 3 μm to approximately 6 μm. The patterned layer or the feature pattern or feature 242 of the alumina-carbon hybrid hard mask 220 is separated by vias, gaps, or spaces which may have a width of approximately 5 nm to approximately 250 nm, approximately 10 nm to approximately 150 nm, or approximately 20 nm to approximately 100 nm. The feature pattern or feature 242 can have an aspect ratio of approximately 20 to approximately 500, approximately 30 to approximately 300, or approximately 40 to approximately 200.

[0059]

[0062] Figures 3A–3F are cross-sectional views of a workpiece 300 at different stages of a process for preparing or forming a device, as described and explained in one or more embodiments herein. The device may be or may include a memory device, a logic device, a microelectronic device, and / or other devices. In one or more embodiments, a method is provided for forming or preparing a device, the method comprising positioning a workpiece 300 inside a process area of ​​a processing chamber, the workpiece 300 comprising a metal or metal nitride layer 304 disposed on or over the substrate 302, a silicon-containing hard mask 330 disposed over the metal or metal nitride layer 304, and a patterned photoresist (PR) layer 340 having a feature pattern of features 342 disposed on the silicon-containing hard mask 330. The method further includes etching a silicon-containing hard mask 330 to have a feature pattern of features 342 of a patterned PR layer 340, removing the patterned PR layer 340 from the silicon-containing hard mask 330, and depositing a carbon hard mask layer 310 at least within the features 342 of the patterned PR layer 340. The method also includes treating the carbon hard mask layer 310 by exposing a workpiece 300 to an SIS process to form an alumina-carbon hybrid hard mask 320 that is denser than the carbon hard mask layer 310, and then etching the silicon-containing hard mask 330 to generate an inverted pattern 332 inside the alumina-carbon hybrid hard mask 320.

[0060]

[0063] The patterned PR layer 340 can be deposited, formed, positioned, or otherwise arranged on the silicon-containing hard mask 330, as shown in Figure 3A. In one or more embodiments, the patterned PR layer 340 can be produced or formed by an extreme ultraviolet (EUV) lithography process or a deep ultraviolet (DUV) lithography process. In one or more embodiments, the patterned PR layer 340 can be an EUV stack containing the PR layer below a bottom ARC (BARC) layer, or include such a stack, to provide a PR / BARC stack. In other embodiments, the patterned PR layer 340 can be a DUV stack containing the PR layer below a BARC layer below a dielectric ARC (DARC) layer, or include such a stack, to provide a PR / BARC / DARC stack.

[0061]

[0064] The metal or metal nitride layer 304 may be or may include metal oxides, metal nitrides, silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof. The metal or metal nitride layer 304 may be or may include a stack disposed on or across the substrate 302. In one or more embodiments, the stack includes alternating layers of silicon oxide and silicon nitride. The substrate 302 may be or may include any type of substrate, including the substrate 102 described above.

[0062]

[0065] In some embodiments, the metal or metal nitride layer 304 may be or include one or more metal layers. In some embodiments, the metal layers may be or include metallic titanium, metallic tantalum, metallic tungsten, alloys thereof, or any combination thereof. In other embodiments, the metal or metal nitride layer 304 may be or include a metal nitride layer, and the metal nitride layer may be or include titanium nitride, tantalum nitride, tungsten nitride, alloys thereof, or any combination thereof. In some embodiments, the metal or metal nitride layer 304 may be or include one or more layers of any kind including the underlying layer 104 described above.

[0063]

[0066] In some embodiments, feature 342 is completely etched over the entire thickness of the silicon-containing hard mask 330, as shown in Figure 3B. The patterned PR layer 340 can then be removed from the workpiece 300. The silicon-containing hard mask 330 may be or include silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof. In one or more embodiments, the silicon-containing hard mask 330 may be or include any type of hard mask, including the silicon-containing hard mask 230 described above. In some embodiments, the silicon-containing hard mask 330 may be etched or removed by exposure of the silicon-containing hard mask 330 to one or more carbon fluoride etching solutions and one or more process gases. The carbon fluoride etching solutions may be or include tetrafluoromethane, trifluoromethane, difluoromethane, monofluoromethane, octafluorocyclobutane, hexafluoro-1,3-butadiene, or any combination thereof. The process gas may be argon, helium, nitrogen (N2), oxygen (O2), or any combination thereof, or may include them.

[0064]

[0067] In one or more embodiments, the patterned PR layer 340 can be removed from the silicon-containing hard mask 330, which involves exposing the patterned PR layer 340 to an etching process. In some embodiments, the etching process involves exposing the patterned PR layer 340 to a combination of one or more halogen-containing compounds and at least one of oxygen (O2), argon, helium, or a combination thereof. The halogen-containing compounds may be or may include chlorine (Cl2), hydrogen bromide (HBr), or any combination thereof. In other embodiments, the patterned PR layer 340 can be removed from the silicon-containing hard mask 330 by exposing the patterned PR layer 340 to a polishing process. The polishing process may be a chemical mechanical polishing (CMP) process.

[0065]

[0068] As shown in Figure 3C, the carbon hard mask layer 310 can be deposited on the upper surface of the patterned PR layer 340 or formed in any other way, with the carbon hard mask layer 310 deposited within the feature pattern of the feature 342 of the patterned PR layer 340. The carbon hard mask layer 310 can have a composition and properties and can be deposited by the same process as the carbon hard mask layer 110 described above or formed in any other way.

[0066]

[0069] As shown in Figure 3D, the carbon hard mask layer 310 can be removed from the top surface of the patterned PR layer 340 before processing the carbon hard mask layer 310 in the SIS process. In one or more embodiments, the carbon hard mask layer 310 is removed from the top surface of the patterned PR layer 340, which includes a polishing process (e.g., CMP).

[0067]

[0070] Figures 3D-3E show the processing or transition of the carbon hard mask layer 310 (Figure 3D) to produce the alumina-carbon hybrid hard mask 320 (Figure 3E) via the SIS process. In the workpiece 300, the SIS process is selective for the carbon hard mask layer 310 and non-reactive or substantially non-reactive for other exposed surfaces and layers, such as the metal or metal nitride layer 304 and the silicon-containing hard mask 330. The alumina-carbon hybrid hard mask 320 has a higher density than the carbon hard mask layer 310. The alumina-carbon hybrid hard mask 320 may have the same composition and properties as the alumina-carbon hybrid hard mask 120 described above.

[0068]

[0071] In one or more embodiments, as shown in Figure 3F, the silicon-containing hard mask 330 can be etched or otherwise removed to generate an inverted pattern 332 inside the alumina-carbon hybrid hard mask 320. In one or more embodiments, the silicon-containing hard mask 330 can be removed by etching the workpiece 300 with inductively coupled plasma (ICP) while maintaining the alumina-carbon hybrid hard mask 320 on the metal or metal nitride layer 304. In some embodiments, the ICP can include or be formed from a mixture of oxygen (O2) and argon.

[0069]

[0072] In other embodiments, the silicon-containing hard mask 330 can be etched or otherwise removed to generate an inverted pattern 332 inside the alumina-carbon hybrid hard mask 320 by other processes. The workpiece 300 can be exposed to a selective removal process or a wet etching process to remove the silicon-containing hard mask 330 while maintaining the alumina-carbon hybrid hard mask 320 on the metal or metal nitride layer 304.

[0070]

[0073] The alumina-carbon hybrid hard mask 320 contains at least aluminum, oxygen, and carbon. In one or more embodiments, the alumina-carbon hybrid hard mask 320 may contain aluminum in the range of about 3 at%, about 4 at%, about 5 at%, about 6 at%, about 8 at%, or about 10 at%, to about 12 at%, about 14 at%, about 15 at%, about 16 at%, about 18 at%, about 20 at%, about 22 at%, or about 25 at%. For example, the alumina-carbon hybrid hard mask 320 may contain aluminum in the range of approximately 3 at% to 25 at%, approximately 3 at% to 20 at%, approximately 5 at% to 20 at%, approximately 8 at% to 20 at%, approximately 10 at% to 20 at%, approximately 12 at% to 20 at%, approximately 15 at% to 20 at%, approximately 18 at% to 20 at%, approximately 3 at% to 15 at%, approximately 5 at% to 15 at%, approximately 8 at% to 15 at%, approximately 10 at% to 15 at%, approximately 12 at% to 15 at%, approximately 14 at% to 15 at%, approximately 3 at% to 10 at%, approximately 5 at% to 10 at%, or approximately 8 at% to 10 at%.

[0071]

[0074] The Alumina Carbon Hybrid Hard Mask 320 can contain oxygen in the range of approximately 3 at%, 4 at%, 5 at%, 6 at%, 8 at%, or 10 at%, to approximately 12 at%, 15 at%, 18 at%, 20 at%, 22 at%, 25 at%, 28 at%, 30 at%, or 35 at%. For example, the alumina-carbon hybrid hard mask 320 has a range of approximately 3 at% to 35 at%, 3 at% to 30 at%, 3 at% to 25 at%, 3 at% to 20 at%, 5 at% to 35 at%, 5 at% to 30 at%, 5 at% to 25 at%, 5 at% to 20 at%, 8 at% to 20 at%, 10 at% to 20 at%, 12 at% to 20 at%, 15 at% to 20 at%, 18 at% to 20 at%, and 5 at% to 3 It can contain oxygen in the range of 0 at%, approximately 8 at% to 30 at%, approximately 10 at% to 30 at%, approximately 12 at% to 30 at%, approximately 15 at% to 30 at%, approximately 18 at% to 30 at%, approximately 3 at% to 15 at%, approximately 5 at% to 15 at%, approximately 8 at% to 15 at%, approximately 10 at% to 15 at%, approximately 12 at% to 15 at%, approximately 14 at% to 15 at%, approximately 3 at% to 10 at%, approximately 5 at% to 10 at%, or approximately 8 at% to 10 at%.

[0072]

[0075] Alumina-carbon hybrid hard mask 320 can contain carbon ranging from approximately 40 at%, 45 at%, 50 at%, 55 at%, 60 at%, or 65 at%, to approximately 70 at%, 75 at%, 80 at%, 85 at%, 90 at%, or 95 at%. For example, the alumina-carbon hybrid hard mask 320 may contain carbon in the range of approximately 40 at% to 90 at%, 50 at% to 90 at%, 60 at% to 90 at%, 70 at% to 90 at%, 80 at% to 90 at%, 40 at% to 75 at%, 50 at% to 75 at%, 60 at% to 75 at%, 70 at% to 75 at%, 40 at% to 60 at%, 45 at% to 60 at%, 50 at% to 60 at%, or 55 at% to 60 at%.

[0073]

[0076] In one or more embodiments, the alumina-carbon hybrid hard mask 320 may contain about 5 at% to about 20 at% aluminum, about 5 at% to about 30 at% oxygen, and about 50 at% to about 90 at% carbon. In some embodiments, the alumina-carbon hybrid hard mask 320 may contain about 10 at% to about 20 at% aluminum, about 10 at% to about 30 at% oxygen, and about 50 at% to about 80 at% carbon. In one or more embodiments, the alumina-carbon hybrid hard mask 320 may contain about 5 at% to about 10 at% aluminum, about 5 at% to about 20 at% oxygen, and about 70 at% to about 90 at% carbon.

[0074]

[0077] The alumina-carbon hybrid hard mask 320 has a thickness in the range of approximately 1 μm to approximately 20 μm, approximately 2 μm to approximately 10 μm, or approximately 3 μm to approximately 6 μm. The alumina-carbon hybrid hard mask 320 can be a patterned layer containing the feature pattern of feature 342 shown in Figure 3F, or may contain such a layer. The feature pattern or feature 342 may have a height less than or equal to the thickness of the alumina-carbon hybrid hard mask 320. Therefore, the feature pattern or feature 342 may have a height in the range of approximately 1 μm to approximately 20 μm, approximately 2 μm to approximately 10 μm, or approximately 3 μm to approximately 6 μm. The patterned layer or the feature pattern or feature 342 of the alumina-carbon hybrid hard mask 320 is separated by vias, gaps, or spaces which may have a width of approximately 5 nm to approximately 250 nm, approximately 10 nm to approximately 150 nm, or approximately 20 nm to approximately 100 nm. The feature pattern or feature 342 can have an aspect ratio of approximately 20 to approximately 500, approximately 30 to approximately 300, or approximately 40 to approximately 200.

[0075]

[0078] Figures 4A–4G are cross-sectional views of a workpiece 400 at different stages of a process for preparing or forming a device, as described and explained in one or more embodiments herein. The device may be or may include a memory device, a logic device, a microelectronic device, and / or other devices. In one or more embodiments, a method is provided for forming or producing a device, the method comprising positioning a workpiece 400 inside a process area of ​​a processing chamber, the workpiece 400 comprising a metal or metal nitride layer 404 disposed on or over a substrate 302, a silicon-containing hard mask 430 disposed over the metal or metal nitride layer 404, and a patterned photoresist (PR) layer 440 having a feature pattern of features 442 disposed on the silicon-containing hard mask 430. The method also includes etching a silicon-containing hard mask 430 to have a feature pattern of features 442 of a patterned PR layer 440, removing the patterned PR layer 440 from the silicon-containing hard mask 430, and depositing a carbon hard mask layer 410 within features 442 of the patterned PR layer 440 and on the upper surface of the patterned PR layer 440. The method further includes depositing a photoresist-anti-reflective coating (PR-ARC) layer 450 on a first portion of the carbon hard mask layer 410, leaving a second portion of the carbon hard mask layer 410 exposed. The method also includes etching a second portion of the carbon hard mask layer 410 while maintaining the PR-ARC layer 450 and the first portion of the carbon hard mask layer 410 on the workpiece 400 during a first mask etching process, and etching the PR-ARC layer 450 while maintaining the first portion of the carbon hard mask layer 410 on the workpiece 400 during a second mask etching process. The method further includes treating a first portion of the carbon hard mask layer 410 by exposing the workpiece 400 to an SIS process to produce an alumina-carbon hybrid hard mask 420 that is denser than the carbon hard mask layer 410.

[0076]

[0079] As shown in Figure 4A, the patterned PR layer 440 can be placed, formed, positioned or otherwise arranged on the silicon-containing hard mask 430. In one or more embodiments, the patterned PR layer 440 can be produced or formed by an extreme ultraviolet (EUV) lithography process or a deep ultraviolet (DUV) lithography process. In one or more embodiments, the patterned PR layer 440 can be an EUV stack containing the PR layer below a bottom ARC (BARC) layer, or include such a stack, to provide a PR / BARC stack. In other embodiments, the patterned PR layer 440 can be a DUV stack containing the PR layer below a BARC layer below a dielectric ARC (DARC) layer, or include such a stack, to provide a PR / BARC / DARC stack.

[0077]

[0080] The metal or metal nitride layer 404 may be or may include metal oxides, metal nitrides, silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof. The metal or metal nitride layer 404 may be or may include a stack disposed on or covering the substrate 402. In one or more embodiments, the stack includes alternating layers of silicon oxide and silicon nitride. The substrate 402 may be or may include any type of substrate, including the substrate 102 described above.

[0078]

[0081] In some embodiments, the metal or metal nitride layer 404 may be or include one or more metal layers. In some embodiments, the metal layers may be or include metallic titanium, metallic tantalum, metallic tungsten, alloys thereof, or any combination thereof. In other embodiments, the metal or metal nitride layer 404 may be or include a metal nitride layer, and the metal nitride layer may be or include titanium nitride, tantalum nitride, tungsten nitride, alloys thereof, or any combination thereof. In some embodiments, the metal or metal nitride layer 404 may be or include one or more layers of any kind including the underlying layer 104 and / or the metal or metal nitride layer described and explained above.

[0079]

[0082] In some embodiments, feature 442 is completely etched over the entire thickness of the silicon-containing hard mask 430, as shown in Figure 4B. The patterned PR layer 440 can then be removed from the workpiece 400. The silicon-containing hard mask 430 may be or include silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof. In one or more embodiments, the silicon-containing hard mask 430 may be or include any type of hard mask, including the silicon-containing hard mask 230 described above. In some embodiments, the silicon-containing hard mask 430 may be etched or removed by exposure of the silicon-containing hard mask 430 to one or more carbon fluoride etching solutions and one or more process gases. The carbon fluoride etching solutions may be or include tetrafluoromethane, trifluoromethane, difluoromethane, monofluoromethane, octafluorocyclobutane, hexafluoro-1,3-butadiene, or any combination thereof. The process gas may be argon, helium, nitrogen (N2), oxygen (O2), or any combination thereof, or may include them.

[0080]

[0083] In one or more embodiments, the patterned PR layer 440 may be from the silicon-containing hard mask 430 and the process involves exposing the patterned PR layer 440 to an etching process. In some embodiments, the etching process involves exposing the patterned PR layer 440 to a combination of one or more halogen-containing compounds and at least one of oxygen (O2), argon, helium, or a combination thereof. The halogen-containing compounds may be or may include chlorine (Cl2), hydrogen bromide (HBr), or any combination thereof. In other embodiments, the patterned PR layer 440 may be removed from the silicon-containing hard mask 430 by exposing the patterned PR layer 440 to a polishing process. The polishing process may be a chemical mechanical polishing (CMP) process.

[0081]

[0084] As shown in Figure 4C, the carbon hard mask layer 410 can be deposited on the upper surface of the patterned PR layer 440 or formed in any other way, with the carbon hard mask layer 410 deposited within the features 442 of the patterned PR layer 440. The carbon hard mask layer 410 can have a composition and properties and can be deposited by the same process as the carbon hard mask layer 110 described above or formed in any other way.

[0082]

[0085] As shown in Figure 4D, the photoresist-anti-reflective coating (PR-ARC) layer 450 can be deposited, formed, or otherwise positioned on one or more first portions of the carbon hard mask layer 410, leaving one or more exposed second portions of the carbon hard mask layer 410. The PR-ARC layer 450 can be produced by an EUV lithography process and / or a DUV lithography process. In one or more embodiments, the PR-ARC layer 450 may be or include a photoresist layer, a bottom anti-reflective coating (BARC) layer, and a dielectric anti-reflective coating (DARC) layer. In other embodiments, the PR-ARC layer 450 may be or include a photoresist layer and a silicon-containing anti-reflective coating (SiARC) layer.

[0083]

[0086] As shown in Figure 4E, during the first mask etching process, a second portion of the carbon hard mask layer 410 is etched or otherwise removed while the PR-ARC layer 450 and a first portion of the carbon hard mask layer 410 are maintained on the workpiece 400. In one or more embodiments, the first mask etching process includes removing the second portion 410 of the carbon hard mask layer and exposing the workpiece 400 to an inductively coupled plasma while maintaining the PR-ARC layer 450 and the first portion 410 of the carbon hard mask layer on the workpiece 400. In some embodiments, the inductively coupled plasma may include or be formed from a mixture of oxygen (O2) and argon.

[0084]

[0087] The PR-ARC layer 450 is etched or otherwise removed during a second mask etching process, as shown in Figure 4F, while retaining a first portion 410 of the carbon hard mask layer on the workpiece 400. The second mask etching process includes removing the PR-ARC layer 450 by exposing the workpiece 400 to a selective removal process or a wet etching process, while retaining a first portion of the carbon hard mask layer 410 on the workpiece 400.

[0085]

[0088] Figures 4F-4G show the treatment or transition of the carbon hard mask layer 410 (Figure 4F) for producing the alumina-carbon hybrid hard mask 420 (Figure 4G) via the SIS process. On the workpiece 400, the SIS process is selective for the carbon hard mask layer 410 and non-reactive or substantially non-reactive for other exposed surfaces and layers, such as the metal or metal nitride layer 404 and the silicon-containing hard mask 430. The alumina-carbon hybrid hard mask 420 has a higher density than the carbon hard mask layer 410. The alumina-carbon hybrid hard mask 420 may have the same composition and properties as the alumina-carbon hybrid hard mask 120 described above.

[0086]

[0089] The alumina-carbon hybrid hard mask 420 contains at least aluminum, oxygen, and carbon. In one or more embodiments, the alumina-carbon hybrid hard mask 420 may contain aluminum ranging from about 3 at%, about 4 at%, about 5 at%, about 6 at%, about 8 at%, or about 10 at%, to about 12 at%, about 14 at%, about 15 at%, about 16 at%, about 18 at%, about 20 at%, about 22 at%, or about 25 at%. For example, the alumina-carbon hybrid hard mask 420 may contain aluminum in the range of approximately 3 at% to 25 at%, approximately 3 at% to 20 at%, approximately 5 at% to 20 at%, approximately 8 at% to 20 at%, approximately 10 at% to 20 at%, approximately 12 at% to 20 at%, approximately 15 at% to 20 at%, approximately 18 at% to 20 at%, approximately 3 at% to 15 at%, approximately 5 at% to 15 at%, approximately 8 at% to 15 at%, approximately 10 at% to 15 at%, approximately 12 at% to 15 at%, approximately 14 at% to 15 at%, approximately 3 at% to 10 at%, approximately 5 at% to 10 at%, or approximately 8 at% to 10 at%.

[0087]

[0090] The Alumina Carbon Hybrid Hard Mask 420 can contain oxygen ranging from approximately 3 at%, 4 at%, 5 at%, 6 at%, 8 at%, or 10 at%, to approximately 12 at%, 15 at%, 18 at%, 20 at%, 22 at%, 25 at%, 28 at%, 30 at%, or 35 at%. For example, the alumina-carbon hybrid hard mask 420 has a range of approximately 3 at% to 35 at%, 3 at% to 30 at%, 3 at% to 25 at%, 3 at% to 20 at%, 5 at% to 35 at%, 5 at% to 30 at%, 5 at% to 25 at%, 5 at% to 20 at%, 8 at% to 20 at%, 10 at% to 20 at%, 12 at% to 20 at%, 15 at% to 20 at%, 18 at% to 20 at%, and 5 at% to 3 It can contain oxygen in the range of 0 at%, approximately 8 at% to 30 at%, approximately 10 at% to 30 at%, approximately 12 at% to 30 at%, approximately 15 at% to 30 at%, approximately 18 at% to 30 at%, approximately 3 at% to 15 at%, approximately 5 at% to 15 at%, approximately 8 at% to 15 at%, approximately 10 at% to 15 at%, approximately 12 at% to 15 at%, approximately 14 at% to 15 at%, approximately 3 at% to 10 at%, approximately 5 at% to 10 at%, or approximately 8 at% to 10 at%.

[0088]

[0091] Alumina-carbon hybrid hard mask 420 can contain carbon ranging from approximately 40 at%, 45 at%, 50 at%, 55 at%, 60 at%, or 65 at%, to approximately 70 at%, 75 at%, 80 at%, 85 at%, 90 at%, or 95 at%. For example, the alumina-carbon hybrid hard mask 420 may contain carbon in the range of approximately 40 at% to 90 at%, 50 at% to 90 at%, 60 at% to 90 at%, 70 at% to 90 at%, 80 at% to 90 at%, 40 at% to 75 at%, 50 at% to 75 at%, 60 at% to 75 at%, 70 at% to 75 at%, 40 at% to 60 at%, 45 at% to 60 at%, 50 at% to 60 at%, or 55 at% to 60 at%.

[0089]

[0092] In one or more embodiments, the alumina-carbon hybrid hard mask 420 may contain about 5 at% to about 20 at% aluminum, about 5 at% to about 30 at% oxygen, and about 50 at% to about 90 at% carbon. In some embodiments, the alumina-carbon hybrid hard mask 420 may contain about 10 at% to about 20 at% aluminum, about 10 at% to about 30 at% oxygen, and about 50 at% to about 80 at% carbon. In one or more embodiments, the alumina-carbon hybrid hard mask 420 may contain about 5 at% to about 10 at% aluminum, about 5 at% to about 20 at% oxygen, and about 70 at% to about 90 at% carbon.

[0090]

[0093] The alumina-carbon hybrid hard mask 420 has a thickness in the range of approximately 1 μm to approximately 20 μm, approximately 2 μm to approximately 10 μm, or approximately 3 μm to approximately 6 μm. The alumina-carbon hybrid hard mask 420 may be a patterned layer containing the feature pattern of feature 442 shown in Figure 4G, or may contain such a layer. The feature pattern or feature 442 may have a height less than or equal to the thickness of the alumina-carbon hybrid hard mask 420. Therefore, the feature pattern or feature 442 may have a height in the range of approximately 1 μm to approximately 20 μm, approximately 2 μm to approximately 10 μm, or approximately 3 μm to approximately 6 μm. The patterned layer or the feature pattern or feature 442 of the alumina-carbon hybrid hard mask 420 is separated by vias, gaps, or spaces which may have a width of approximately 5 nm to approximately 250 nm, approximately 10 nm to approximately 150 nm, or approximately 20 nm to approximately 100 nm. The feature pattern or feature 442 can have an aspect ratio of approximately 20 to approximately 500, approximately 30 to approximately 300, or approximately 40 to approximately 200.

[0091]

[0094] Most conventional chemical vapor deposition (CVD) or atomic layer deposition (ALD) chambers can be used as processing chambers suitable for carrying out the SIS process described herein. One example of a processing chamber that can be adapted to benefit from the SIS process is the CENTRIS® Sym3, commercially available from the applicant. TM This is an etching chamber. One embodiment of a tool or system that benefits from the SIS process is the iSprint, which is commercially available from the applicant. TM This is a Centura® system or Endura® system that uses an ALD / CVD SSW chamber.

[0092]

[0095] Embodiments of this disclosure further relate to one or more of the following Examples 1 to 185.

[0093]

[0096] Example 1. A method for processing a carbon hard mask layer, comprising: positioning a workpiece inside a process area of ​​a processing chamber, wherein the workpiece includes a carbon hard mask layer positioned on or throughout a lower layer; and processing the carbon hard mask layer by exposing the workpiece to a sequential infiltration synthesis (SIS) process to produce an alumina-carbon hybrid hard mask denser than the carbon hard mask layer, wherein the SIS process comprises one or more infiltration cycles, each of which includes: exposing the carbon hard mask layer to an aluminum precursor; infiltrating the carbon hard mask layer with the aluminum precursor through pores contained in the carbon hard mask layer; purging the process area to remove gaseous residue containing the aluminum precursor; exposing the carbon hard mask layer to an oxidizing agent; infiltrating the carbon hard mask layer with the oxidizing agent through pores contained in the carbon hard mask layer to produce an alumina coating positioned on the inner surface of the carbon hard mask layer; and purging the process area to remove gaseous residue containing the oxidizing agent.

[0094]

[0097] Example 2. The method according to Example 1, wherein the carbon hard mask layer has a thickness of approximately 1 μm to approximately 20 μm.

[0095]

[0098] Example 3. The method according to Example 1 or 2, wherein the carbon hard mask layer is a patterned layer.

[0096]

[0099] Example 4. The method according to any one of Examples 1 to 3, wherein the patterned layer includes features having a height of approximately 1 μm to approximately 20 μm.

[0097]

[0100] Example 5. The method according to any one of Examples 1 to 4, wherein the patterned layer includes features separated by vias, gaps, or spaces having a width of approximately 5 nm to approximately 250 nm.

[0098]

[0101] Example 6. The method according to any one of Examples 1 to 5, wherein the patterned layer includes features having an aspect ratio of approximately 20 to approximately 500.

[0099]

[0102] Example 7. The method according to any one of Examples 1 to 6, wherein the carbon hard mask layer comprises a carbon-containing material having polar functional groups, and the alumina coating is disposed on the inner surface having polar functional groups.

[0100]

[0103] Example 8. The method according to Example 7, wherein the polar functional group includes a CH group, a CO group, a C=O group, or any combination thereof.

[0101]

[0104] Example 9. The method according to any one of Examples 1 to 8, wherein the carbon hard mask layer is deposited by a thermochemical vapor deposition (CVD) process, a plasma-enhanced CVD (PE-CVD) process, a fluid CVD (FCVD) process, or a spin-on process.

[0102]

[0105] Example 10. The method according to any one of Examples 1 to 9, wherein the carbon hard mask layer contains approximately 30 atomic percent (at%) to approximately 80 at% carbon, approximately 10 at% to approximately 50 at% hydrogen, and approximately 10 at% to approximately 20 at% oxygen.

[0103]

[0106] Example 11. The method according to any one of Examples 1 to 10, wherein the alumina-carbon hybrid hard mask contains approximately 5 at% to approximately 20 at% aluminum and approximately 5 at% to approximately 30 at% oxygen.

[0104]

[0107] Example 12. The method according to any one of Examples 1 to 11, wherein the alumina-carbon hybrid hard mask further contains about 50 at% to about 90 at% carbon.

[0105]

[0108] Example 13. The method according to any one of Examples 1 to 12, wherein the lower layer comprises a metal oxide, a metal nitride, silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof.

[0106]

[0109] Example 14. The method according to any one of Examples 1 to 13, wherein the lower layer includes a stack disposed on or across the substrate.

[0107]

[0110] Example 15. The method according to Example 14, wherein the stack comprises alternating layers of silicon oxide and silicon nitride.

[0108]

[0111] Example 16. The method according to any one of Examples 1 to 15, wherein the aluminum precursor comprises an alkylaluminum compound.

[0109]

[0112] Example 17. The method according to any one of Examples 1 to 16, wherein the oxidizing agent comprises water, ozone, atomic oxygen, oxygen plasma, hydrogen peroxide, or any combination thereof.

[0110]

[0113] Example 18. The method according to any one of Examples 1 to 17, wherein the aluminum precursor comprises trimethylaluminum and the oxidizing agent comprises water.

[0111]

[0114] Example 19. The method according to any one of Examples 1 to 18, wherein the infiltration cycle is repeated 2 to approximately 50 times during the SIS process.

[0112]

[0115] Example 20. The method according to any one of Examples 1 to 19, wherein during the SIS process, the process area of ​​the processing chamber is at a pressure of approximately 0.01 Torr to approximately 250 Torr.

[0113]

[0116] Example 21. The method according to any one of Examples 1 to 20, wherein, between each infiltration cycle, the carbon hard mask layer is exposed to the aluminum precursor for about 1 to 10 minutes, during which time the aluminum precursor is infiltrated into the carbon hard mask layer.

[0114]

[0117] Example 22. The method according to any one of Examples 1 to 21, wherein, between each infiltration cycle, the carbon hard mask layer is exposed to a purge gas for about 1 minute to about 30 minutes, during which the process area is purged to remove gaseous residues containing aluminum precursors.

[0115]

[0118] Example 23. The method according to any one of Examples 1 to 22, wherein the carbon hard mask layer is exposed to the oxidizing agent for about 1 to 10 minutes between each penetration cycle, during which time the oxidizing agent is allowed to penetrate the carbon hard mask layer.

[0116]

[0119] Example 24. The method according to any one of Examples 1 to 23, wherein, between each infiltration cycle, the carbon hard mask layer is exposed to a purge gas for about 1 minute to about 30 minutes, during which the process area is purged to remove gaseous residues containing the oxidizing agent.

[0117]

[0120] Example 25. A method for forming a device, comprising positioning a workpiece within a process area of ​​a processing chamber, wherein the workpiece includes a carbon hard mask layer disposed on or over a lower layer, a silicon-containing hard mask disposed on or over the carbon hard mask layer, and a patterned photoresist layer having a feature pattern disposed on the silicon-containing hard mask; etching the silicon-containing hard mask and the carbon hard mask layer so that each has a feature pattern of the patterned photoresist layer; processing the carbon hard mask layer by exposing the workpiece to a sequential penetration synthesis (SIS) process to produce an alumina-carbon hybrid hard mask with a density greater than that of the carbon hard mask layer; and then etching the lower layer so that it has a feature pattern of the patterned photoresist layer.

[0118]

[0121] Example 26. The method according to Example 25, wherein the SIS process comprises one or more infiltration cycles, each of which includes exposing a carbon hard mask layer to an aluminum precursor, infiltrating the carbon hard mask layer with the aluminum precursor through pores contained in the carbon hard mask layer, purging the process area to remove gaseous residue containing the aluminum precursor, exposing the carbon hard mask layer to an oxidizing agent, infiltrating the carbon hard mask layer with the oxidizing agent through pores contained in the carbon hard mask layer to produce an alumina coating disposed on the inner surface of the carbon hard mask layer, and purging the process area to remove gaseous residue containing the oxidizing agent.

[0119]

[0122] Example 27. The method according to Example 25 or 26, wherein the aluminum precursor comprises an alkylaluminum compound.

[0120]

[0123] Example 28. The method according to any one of Examples 25 to 27, wherein the oxidizing agent comprises water, ozone, atomic oxygen, oxygen plasma, hydrogen peroxide, or any combination thereof.

[0121]

[0124] Example 29. The method according to any one of Examples 25 to 28, wherein the aluminum precursor contains trimethylaluminum and the oxidizing agent contains water.

[0122]

[0125] Example 30. The method according to any one of Examples 25-29, wherein the infiltration cycle is repeated 2 to approximately 50 times during the SIS process.

[0123]

[0126] Example 31. The method according to any one of Examples 25-30, wherein during the SIS process, the process area of ​​the processing chamber is at a pressure of approximately 0.01 Torr to approximately 250 Torr.

[0124]

[0127] Example 32. The method according to any one of Examples 25 to 31, wherein, between each infiltration cycle, the carbon hard mask layer is exposed to the aluminum precursor for about 1 to 10 minutes, during which time the aluminum precursor is infiltrated into the carbon hard mask layer.

[0125]

[0128] Example 33. The method according to any one of Examples 25 to 32, wherein, between each infiltration cycle, the carbon hard mask layer is exposed to a purge gas for about 1 minute to about 30 minutes, during which the process area is purged to remove gaseous residues containing aluminum precursors.

[0126]

[0129] Example 34. The method according to any one of Examples 25 to 33, wherein the carbon hard mask layer is exposed to the oxidizing agent for about 1 to 10 minutes between each penetration cycle, during which time the oxidizing agent is allowed to penetrate the carbon hard mask layer.

[0127]

[0130] Example 35. The method according to any one of Examples 25 to 34, wherein, between each infiltration cycle, the carbon hard mask layer is exposed to a purge gas for about 1 minute to about 30 minutes, during which the process area is purged to remove gaseous residues containing the oxidizing agent.

[0128]

[0131] Example 36. The method according to any one of Examples 25 to 35, wherein the patterned photoresist layer is produced by an extreme ultraviolet (EUV) lithography process or a deep ultraviolet (DUV) lithography process.

[0129]

[0132] Example 37. The method according to any one of Examples 25 to 36, wherein the silicon-containing hard mask comprises silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof.

[0130]

[0133] Example 38. The method according to any one of Examples 25 to 37, wherein the device is a memory device, a logic device, or a microelectronic device.

[0131]

[0134] Example 39. The method according to any one of Examples 25-38, wherein the feature pattern is completely etched over the entire thickness of the silicon-containing hard mask.

[0132]

[0135] Example 40. The method according to any one of Examples 25 to 39, further comprising etching a silicon-containing hard mask, or exposing a silicon-containing hard mask to a fluorocarbon etching solution and a process gas.

[0133]

[0136] Example 41. The method according to Example 40, wherein the carbon fluoride etching solution comprises tetrafluoromethane, trifluoromethane, difluoromethane, monofluoromethane, octafluorocyclobutane, hexafluoro-1,3-butadiene, or any combination thereof, and the process gas comprises argon, helium, nitrogen (N2), oxygen (O2), or any combination thereof.

[0134]

[0137] Example 42. The method according to any one of Examples 25-41, wherein the feature pattern is completely etched over the entire thickness of the carbon hard mask layer.

[0135]

[0138] Example 43. The method according to any one of Examples 25 to 42, further comprising etching the carbon hard mask layer and exposing the carbon hard mask layer to an etching gas and a passivation gas.

[0136]

[0139] Example 44. The method according to Example 43, wherein the etching gas comprises argon, oxygen, or a combination thereof, and the passivation gas comprises methane, sulfur dioxide, carbonyl sulfide, or any combination thereof.

[0137]

[0140] Example 45. The method according to any one of Examples 25 to 44, wherein the feature pattern is partially etched to the thickness of the underlying layer.

[0138]

[0141] Example 46. The method according to any one of Examples 25 to 45, further comprising partially etching the underlying layer or exposing the underlying layer to a carbon fluoride etching solution and a process gas.

[0139]

[0142] Example 47. The method according to Example 46, wherein the carbon fluoride etching solution comprises tetrafluoromethane, trifluoromethane, difluoromethane, monofluoromethane, octafluorocyclobutane, hexafluoro-1,3-butadiene, or any combination thereof, and the process gas comprises argon, helium, nitrogen (N2), oxygen (O2), or any combination thereof.

[0140]

[0143] Example 48. The method according to any one of Examples 25 to 47, wherein the carbon hard mask layer has a thickness of approximately 1 μm to approximately 20 μm.

[0141]

[0144] Example 49. The method according to any one of Examples 25 to 48, wherein the carbon hard mask layer is a patterned layer.

[0142]

[0145] Example 50. The method according to any one of Examples 25 to 49, wherein the patterned layer includes features having a height of approximately 1 μm to approximately 20 μm.

[0143]

[0146] Example 51. The method according to any one of Examples 25 to 50, wherein the patterned layer includes features separated by vias, gaps, or spaces having a width of approximately 5 nm to approximately 250 nm.

[0144]

[0147] Example 52. The method according to any one of Examples 25 to 51, wherein the patterned layer includes features having an aspect ratio of about 20 to about 500.

[0145]

[0148] Example 53. The method according to any one of Examples 25 to 52, wherein the carbon hard mask layer comprises a carbon-containing material having polar functional groups, and the alumina coating is disposed on the inner surface having polar functional groups.

[0146]

[0149] Example 54. The method according to Example 53, wherein the polar functional group comprises a CH group, a CO group, a C=O group, or any combination thereof.

[0147]

[0150] Example 55. The method according to any one of Examples 25 to 54, wherein the carbon hard mask layer is deposited by a thermochemical vapor deposition (CVD) process, a plasma-enhanced CVD (PE-CVD) process, a fluid CVD (FCVD) process, or a spin-on process.

[0148]

[0151] Example 56. The method according to any one of Examples 25 to 55, wherein the carbon hard mask layer contains about 30 atomic percent (at%) to about 80 at% carbon, about 10 at% to about 50 at% hydrogen, and about 10 at% to about 20 at% oxygen.

[0149]

[0152] Example 57. The method according to any one of Examples 25 to 56, wherein the alumina-carbon hybrid hard mask contains approximately 5 at% to approximately 20 at% aluminum and approximately 5 at% to approximately 30 at% oxygen.

[0150]

[0153] Example 58. The method according to any one of Examples 25 to 57, wherein the alumina-carbon hybrid hard mask further contains about 50 at% to about 90 at% carbon.

[0151]

[0154] Example 59. The method according to any one of Examples 25 to 58, wherein the lower layer comprises a metal oxide, a metal nitride, silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof.

[0152]

[0155] Example 60. The method according to any one of Examples 25 to 59, wherein the lower layer includes a stack disposed on or across the substrate.

[0153]

[0156] Example 61. The method according to Example 60, wherein the stack comprises alternating layers of silicon oxide and silicon nitride.

[0154]

[0157] Example 62. A method for forming a device, comprising positioning a workpiece within a process area of ​​a processing chamber, wherein the workpiece includes a metal or metal nitride layer disposed on or over the substrate, a silicon-containing hard mask disposed on or over the metal or metal nitride layer, and a patterned photoresist layer having a feature pattern disposed on the silicon-containing hard mask; etching the silicon-containing hard mask to have a feature pattern in the patterned photoresist layer; removing the patterned photoresist layer from the silicon-containing hard mask; depositing a carbon hard mask layer at least within the feature pattern of the patterned photoresist layer; processing the carbon hard mask layer by exposing the workpiece to a sequential penetration synthesis (SIS) process to produce an alumina-carbon hybrid hard mask with a density greater than that of the carbon hard mask layer; and then etching the silicon-containing hard mask to produce an inverted pattern inside the alumina-carbon hybrid hard mask.

[0155]

[0158] Example 63. The method according to Example 62, wherein the SIS process comprises one or more infiltration cycles, each of which includes exposing a carbon hard mask layer to an aluminum precursor, infiltrating the carbon hard mask layer with the aluminum precursor through pores contained in the carbon hard mask layer, purging the process area to remove gaseous residue containing the aluminum precursor, exposing the carbon hard mask layer to an oxidizing agent, infiltrating the carbon hard mask layer with the oxidizing agent through pores contained in the carbon hard mask layer to produce an alumina coating disposed on the inner surface of the carbon hard mask layer, and purging the process area to remove gaseous residue containing the oxidizing agent.

[0156]

[0159] Example 64. The method according to Example 62 or 63, wherein the aluminum precursor comprises an alkylaluminum compound.

[0157]

[0160] Example 65. The method according to any one of Examples 62 to 64, wherein the oxidizing agent comprises water, ozone, atomic oxygen, oxygen plasma, hydrogen peroxide, or any combination thereof.

[0158]

[0161] Example 66. The method according to any one of Examples 62 to 65, wherein the aluminum precursor contains trimethylaluminum and the oxidizing agent contains water.

[0159]

[0162] Example 67. The method according to any one of Examples 62-66, wherein the infiltration cycle is repeated 2 to approximately 50 times during the SIS process.

[0160]

[0163] Example 68. The method according to any one of Examples 62-67, wherein during the SIS process, the process area of ​​the processing chamber is at a pressure of approximately 0.01 Torr to approximately 250 Torr.

[0161]

[0164] Example 69. The method according to any one of Examples 62 to 68, wherein the carbon hard mask layer is exposed to the aluminum precursor for about 1 to 10 minutes, while the aluminum precursor is impregnated into the carbon hard mask layer between each impregnation cycle.

[0162]

[0165] Example 70. The method according to any one of Examples 62-69, wherein, between each infiltration cycle, the carbon hard mask layer is exposed to a purge gas for about 1 minute to about 30 minutes, during which the process area is purged to remove gaseous residues containing aluminum precursors.

[0163]

[0166] Example 71. The method according to any one of Examples 62 to 70, wherein the carbon hard mask layer is exposed to the oxidizing agent for about 1 to 10 minutes between each penetration cycle, during which time the oxidizing agent is allowed to penetrate the carbon hard mask layer.

[0164]

[0167] Example 72. The method according to any one of Examples 62 to 71, wherein, between each infiltration cycle, the carbon hard mask layer is exposed to a purge gas for about 1 minute to about 30 minutes, during which the process area is purged to remove gaseous residues containing the oxidizing agent.

[0165]

[0168] Example 73. The method according to any one of Examples 62 to 72, wherein the patterned photoresist layer is produced by an extreme ultraviolet (EUV) lithography process or a deep ultraviolet (DUV) lithography process.

[0166]

[0169] Example 74. The method according to any one of Examples 62 to 73, wherein the silicon-containing hard mask comprises silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof.

[0167]

[0170] Example 75. The method according to any one of Examples 62 to 74, wherein the device is a memory device, a logic device, or a microelectronic device.

[0168]

[0171] Example 76. The method according to any one of Examples 62-75, wherein the feature pattern is completely etched over the entire thickness of the silicon-containing hard mask.

[0169]

[0172] Example 77. The method according to any one of Examples 62 to 76, further comprising etching a silicon-containing hard mask, or exposing a silicon-containing hard mask to a fluorocarbon etching solution and a process gas.

[0170]

[0173] Example 78. The method according to Example 77, wherein the carbon fluoride etching solution comprises tetrafluoromethane, trifluoromethane, difluoromethane, monofluoromethane, octafluorocyclobutane, hexafluoro-1,3-butadiene, or any combination thereof, and the process gas comprises argon, helium, nitrogen (N2), oxygen (O2), or any combination thereof.

[0171]

[0174] Example 79. The method according to any one of Examples 62 to 78, wherein removing the patterned photoresist layer from the silicon-containing hard mask includes exposing the patterned photoresist layer to an etching process.

[0172]

[0175] Example 80. The method according to Example 79, wherein the etching process comprises exposing a patterned photoresist layer to a combination of a halogen-containing compound and at least one of oxygen (O2), argon, helium, or a combination thereof.

[0173]

[0176] Example 81. The method according to Example 80, wherein the halogen-containing compound comprises chlorine (Cl2), hydrogen bromide (HBr), or any combination thereof.

[0174]

[0177] Example 82. The method according to any one of Examples 62 to 81, wherein removing the patterned photoresist layer from the silicon-containing hard mask includes exposing the patterned photoresist layer to a polishing process.

[0175]

[0178] Example 83. The method according to Example 82, wherein the polishing process includes a chemical mechanical polishing (CMP) process.

[0176]

[0179] Example 84. The method according to any one of Examples 62 to 83, further comprising depositing a carbon hard mask layer on top of a patterned photoresist layer, and between them, depositing the carbon hard mask layer within the feature pattern of the patterned photoresist layer.

[0177]

[0180] Example 85. The method according to Example 84, further comprising removing the carbon hard mask layer from the top surface of the patterned photoresist layer before processing the carbon hard mask layer in the SIS process.

[0178]

[0181] Example 86. The method of Example 85, wherein the carbon hard mask layer is removed from the top surface of the patterned photoresist layer, the polishing process being included.

[0179]

[0182] Example 87. The method according to any one of Examples 62 to 86, wherein the carbon hard mask layer has a thickness of approximately 1 μm to approximately 20 μm.

[0180]

[0183] Example 88. The method according to any one of Examples 62 to 87, wherein the carbon hard mask layer is a patterned layer.

[0181]

[0184] Example 89. The method according to Example 88, wherein the patterned layer includes features having a height of approximately 1 μm to approximately 20 μm.

[0182]

[0185] Example 90. The method according to Example 88 or 89, wherein the patterned layer includes features separated by vias, gaps, or spaces having a width of approximately 5 nm to approximately 250 nm.

[0183]

[0186] Example 91. The method according to any one of Examples 88-90, wherein the patterned layer includes features having an aspect ratio of about 20 to about 500.

[0184]

[0187] Example 92. The method according to any one of Examples 62 to 91, wherein the carbon hard mask layer comprises a carbon-containing material having polar functional groups, and the alumina coating is disposed on the inner surface having polar functional groups.

[0185]

[0188] Example 93. The method according to Example 92, wherein the polar functional group comprises a CH group, a CO group, a C=O group, or any combination thereof.

[0186]

[0189] Example 94. The method according to any one of Examples 62 to 93, wherein the carbon hard mask layer is deposited by a thermochemical vapor deposition (CVD) process, a plasma CVD (PE-CVD) process, a fluidized CVD (FCVD) process, or a spin-on process.

[0187]

[0190] Example 95. The method according to any one of Examples 62 to 94, wherein the carbon hard mask layer contains about 30 atomic percent (at%) to about 80 at% carbon, about 10 at% to about 50 at% hydrogen, and about 10 at% to about 20 at% oxygen.

[0188]

[0191] Example 96. The method according to any one of Examples 62 to 95, wherein the alumina-carbon hybrid hard mask contains approximately 5 at% to approximately 20 at% aluminum and approximately 5 at% to approximately 30 at% oxygen.

[0189]

[0192] Example 97. The method according to any one of Examples 62 to 96, wherein the alumina-carbon hybrid hard mask further contains about 50 at% to about 90 at% carbon.

[0190]

[0193] Example 98. The method according to any one of Examples 62 to 97, further comprising etching a silicon-containing hard mask to generate an inverted pattern inside the alumina-carbon hybrid hard mask, and removing the silicon-containing hard mask by exposing the workpiece to inductively coupled plasma (ICP) while maintaining the alumina-carbon hybrid hard mask on a metal or metal nitride layer.

[0191]

[0194] Example 99. The method according to Example 98, wherein the ICP comprises a mixture of oxygen (O2) and argon.

[0192]

[0195] Example 100. The method according to any one of Examples 62 to 99, further comprising etching a silicon-containing hard mask to generate an inversion pattern inside the alumina-carbon hybrid hard mask, and removing the silicon-containing hard mask by exposing a workpiece to a selective removal process or a wet etching process while maintaining the alumina-carbon hybrid hard mask on a metal or metal nitride layer.

[0193]

[0196] Example 101. The method according to any one of Examples 62 to 100, wherein the metal or metal nitride layer is a metal layer, and the metal layer comprises metallic titanium, metallic tantalum, metallic tungsten, an alloy thereof, or any combination thereof.

[0194]

[0197] Example 102. The method according to any one of Examples 62 to 101, wherein the metal or metal nitride layer is a metal nitride layer, and the metal nitride layer comprises titanium nitride, tantalum nitride, tungsten nitride, an alloy thereof, or any combination thereof.

[0195]

[0198] Example 103. A method for forming a device, comprising positioning a workpiece within a process area of ​​a processing chamber, wherein the workpiece includes a metal or metal nitride layer disposed on or over the substrate, a silicon-containing hard mask disposed on or over the metal or metal nitride layer, and a patterned photoresist layer having a feature pattern disposed on the silicon-containing hard mask; etching the silicon-containing hard mask to have a feature pattern in the patterned photoresist layer; removing the patterned photoresist layer from the silicon-containing hard mask; and placing the carbon hard mask layer within the feature pattern of the patterned photoresist layer and on the upper surface of the patterned photoresist layer. A method comprising: depositing a photoresist-anti-reflective coating (PR-ARC) layer on a first portion of a carbon hard mask layer, leaving a second portion of the exposed carbon hard mask layer intact; etching the second portion of the carbon hard mask layer while maintaining the PR-ARC layer and the first portion of the carbon hard mask layer on the workpiece during a first mask etching process; etching the PR-ARC layer while maintaining the first portion of the carbon hard mask layer on the workpiece during a second mask etching process; and treating the first portion of the carbon hard mask layer by exposing the workpiece to a sequential penetration synthesis (SIS) process to produce an alumina-carbon hybrid hard mask with a density higher than that of the carbon hard mask layer.

[0196]

[0199] Example 104. The method according to Example 103, wherein the SIS process comprises one or more infiltration cycles, each of which includes exposing a carbon hard mask layer to an aluminum precursor, infiltrating the carbon hard mask layer with the aluminum precursor through pores contained in the carbon hard mask layer, purging the process area to remove gaseous residue containing the aluminum precursor, exposing the carbon hard mask layer to an oxidizing agent, infiltrating the carbon hard mask layer with the oxidizing agent through pores contained in the carbon hard mask layer to produce an alumina coating disposed on the inner surface of the carbon hard mask layer, and purging the process area to remove gaseous residue containing the oxidizing agent.

[0197]

[0200] Example 105. The method according to Example 103 or 104, wherein the aluminum precursor comprises an alkylaluminum compound.

[0198]

[0201] Example 106. The method according to any one of Examples 103 to 105, wherein the oxidizing agent comprises water, ozone, atomic oxygen, oxygen plasma, hydrogen peroxide, or any combination thereof.

[0199]

[0202] Example 107. The method according to any one of Examples 103 to 106, wherein the aluminum precursor comprises trimethylaluminum and the oxidizing agent comprises water.

[0200]

[0203] Example 108. The method according to any one of Examples 103 to 107, wherein the infiltration cycle is repeated 2 to approximately 50 times during the SIS process.

[0201]

[0204] Example 109. The method according to any one of Examples 103 to 108, wherein during the SIS process, the process area of ​​the processing chamber is at a pressure of approximately 0.01 Torr to approximately 250 Torr.

[0202]

[0205] Example 110. The method according to any one of Examples 103 to 109, wherein, between each infiltration cycle, the carbon hard mask layer is exposed to the aluminum precursor for about 1 to 10 minutes, during which time the aluminum precursor is infiltrated into the carbon hard mask layer.

[0203]

[0206] Example 111. The method according to any one of Examples 103 to 110, wherein, between each infiltration cycle, the carbon hard mask layer is exposed to a purge gas for about 1 minute to about 30 minutes, during which the process area is purged to remove gaseous residues containing aluminum precursors.

[0204]

[0207] Example 112. The method according to any one of Examples 103 to 111, wherein the carbon hard mask layer is exposed to the oxidizing agent for about 1 to 10 minutes between each penetration cycle, during which time the oxidizing agent is allowed to penetrate the carbon hard mask layer.

[0205]

[0208] Example 113. The method according to any one of Examples 103 to 112, wherein, between each infiltration cycle, the carbon hard mask layer is exposed to a purge gas for about 1 minute to about 30 minutes, during which the process area is purged to remove gaseous residues containing the oxidizing agent.

[0206]

[0209] Example 114. The method according to any one of Examples 103 to 113, wherein the patterned photoresist layer is produced by an extreme ultraviolet (EUV) lithography process or a deep ultraviolet (DUV) lithography process.

[0207]

[0210] Example 115. The method according to any one of Examples 103 to 114, wherein the silicon-containing hard mask comprises silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof.

[0208]

[0211] Example 116. The method according to any one of Examples 103 to 115, wherein the device is a memory device, a logic device, or a microelectronic device.

[0209]

[0212] Example 117. The method according to any one of Examples 103 to 116, wherein the feature pattern is completely etched over the entire thickness of the silicon-containing hard mask.

[0210]

[0213] Example 118. The method according to any one of Examples 103 to 117, further comprising etching a silicon-containing hard mask, or exposing a silicon-containing hard mask to a fluorocarbon etching solution and a process gas.

[0211]

[0214] Example 119. The method according to Example 118, wherein the carbon fluoride etching solution comprises tetrafluoromethane, trifluoromethane, difluoromethane, monofluoromethane, octafluorocyclobutane, hexafluoro-1,3-butadiene, or any combination thereof, and the process gas comprises argon, helium, nitrogen (N2), oxygen (O2), or any combination thereof.

[0212]

[0215] Example 120. The method according to any one of Examples 103 to 119, wherein removing the patterned photoresist layer from a silicon-containing hard mask is performed by exposing the patterned photoresist layer to an etching process.

[0213]

[0216] Example 121. The method according to Example 120, wherein the etching process comprises exposing a patterned photoresist layer to a combination of a halogen-containing compound and at least one of oxygen (O2), argon, helium, or a combination thereof.

[0214]

[0217] Example 122. The method according to Example 121, wherein the halogen-containing compound comprises chlorine (Cl2), hydrogen bromide (HBr), or any combination thereof.

[0215]

[0218] Example 123. The method according to any one of Examples 103 to 122, wherein removing the patterned photoresist layer from the silicon-containing hard mask includes exposing the patterned photoresist layer to a polishing process.

[0216]

[0219] Example 124. The method according to Example 123, wherein the polishing process includes a chemical mechanical polishing (CMP) process.

[0217]

[0220] Example 125. The method according to any one of Examples 103 to 124, wherein the first mask etching process includes exposing the workpiece to inductively coupled plasma (ICP) during which a second portion of the carbon hard mask layer is removed, while retaining the PR-ARC layer and the first portion of the carbon hard mask layer on the workpiece.

[0218]

[0221] Example 126. The method according to Example 125, wherein the ICP comprises a mixture of oxygen (O2) and argon.

[0219]

[0222] Example 127. The method according to any one of Examples 103 to 126, wherein a second mask etching process includes removing the PR-ARC layer by exposing the workpiece to a selective removal process or a wet etching process while maintaining a first portion of the carbon hard mask layer on the workpiece.

[0220]

[0223] Example 128. The method according to any one of Examples 103 to 127, wherein the carbon hard mask layer has a thickness of approximately 1 μm to approximately 20 μm.

[0221]

[0224] Example 129. The method according to any one of Examples 103 to 128, wherein the carbon hard mask layer is a patterned layer.

[0222]

[0225] Example 130. The method according to Example 129, wherein the patterned layer includes features having a height of approximately 1 μm to approximately 20 μm.

[0223]

[0226] Example 131. The method according to Example 129 or 130, wherein the patterned layer includes features separated by vias, gaps, or spaces having a width of approximately 5 nm to approximately 250 nm.

[0224]

[0227] Example 132. The method according to any one of Examples 129 to 131, wherein the patterned layer includes features having an aspect ratio of approximately 20 to approximately 500.

[0225]

[0228] Example 133. The method according to any one of Examples 103 to 132, wherein the carbon hard mask layer comprises a carbon-containing material having polar functional groups, and the alumina coating is disposed on the inner surface having polar functional groups.

[0226]

[0229] Example 134. The method according to Example 133, wherein the polar functional group comprises a CH group, a CO group, a C=O group, or any combination thereof.

[0227]

[0230] Example 135. The method according to any one of Examples 103 to 134, wherein the carbon hard mask layer is deposited by a thermochemical vapor deposition (CVD) process, a plasma-enhanced CVD (PE-CVD) process, a fluid CVD (FCVD) process, or a spin-on process.

[0228]

[0231] Example 136. The method according to any one of Examples 103 to 135, wherein the carbon hard mask layer contains about 30 atomic percent (at%) to about 80 at% carbon, about 10 at% to about 50 at% hydrogen, and about 10 at% to about 20 at% oxygen.

[0229]

[0232] Example 137. The method according to any one of Examples 103 to 136, wherein the alumina-carbon hybrid hard mask contains approximately 5 at% to approximately 20 at% aluminum and approximately 5 at% to approximately 30 at% oxygen.

[0230]

[0233] Example 138. The method according to any one of Examples 103 to 137, wherein the alumina-carbon hybrid hard mask further contains about 50 at% to about 90 at% carbon.

[0231]

[0234] Example 139. The method according to any one of Examples 103 to 138, wherein the metal or metal nitride layer is a metal layer, and the metal layer comprises metallic titanium, metallic tantalum, metallic tungsten, an alloy thereof, or any combination thereof.

[0232]

[0235] Example 140. The method according to any one of Examples 103 to 139, wherein the metal or metal nitride layer is a metal nitride layer, and the metal nitride layer comprises titanium nitride, tantalum nitride, tungsten nitride, an alloy thereof, or any combination thereof.

[0233]

[0236] Example 141. The method according to any one of Examples 103 to 140, wherein the PR-ARC layer is produced by an extreme ultraviolet (EUV) lithography process.

[0234]

[0237] Example 142. The method according to any one of Examples 103 to 141, wherein the PR-ARC layer comprises a photoresist layer, a bottom anti-reflective coating (BARC) layer, and a dielectric anti-reflective coating (DARC) layer.

[0235]

[0238] Example 143. The method according to any one of Examples 103 to 142, wherein the PR-ARC layer comprises a photoresist layer and a silicon-containing anti-reflective coating (SiARC) layer.

[0236]

[0239] Example 144. A workpiece and / or device prepared, manufactured, processed, or otherwise created by any one of Examples 1 to 143 and / or as shown in any of the drawings.

[0237]

[0240] Example 145. A workpiece and / or device comprising a lower layer disposed on a substrate and an alumina-carbon hybrid hard mask disposed on the lower layer, wherein the alumina-carbon hybrid hard mask includes features.

[0238]

[0241] Example 146. The workpiece and / or device according to Example 145, wherein the alumina-carbon hybrid hard mask has a thickness of approximately 1 μm to approximately 20 μm.

[0239]

[0242] Example 147. The workpiece and / or device according to Example 145 or 146, wherein the alumina-carbon hybrid hard mask includes features having a height of approximately 1 μm to approximately 20 μm.

[0240]

[0243] Example 148. A workpiece and / or device according to any one of Examples 145 to 147, wherein the alumina-carbon hybrid hard mask includes features separated by vias, gaps, or spaces having a width of approximately 5 nm to approximately 250 nm.

[0241]

[0244] Example 149. A workpiece and / or device according to any one of Examples 145 to 148, wherein the features have an aspect ratio of approximately 20 to approximately 500.

[0242]

[0245] Example 150. A workpiece and / or device according to any one of Examples 145 to 149, wherein the alumina-carbon hybrid hard mask contains approximately 5 at% to approximately 20 at% aluminum and approximately 5 at% to approximately 30 at% oxygen.

[0243]

[0246] Example 151. A workpiece and / or device according to any one of Examples 145-150, wherein the alumina-carbon hybrid hard mask further contains about 50 at% to about 90 at% carbon.

[0244]

[0247] Example 152. A workpiece and / or device according to any one of Examples 145 to 151, wherein the lower layer comprises a metal oxide, a metal nitride, silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof.

[0245]

[0248] Example 153. A workpiece and / or device according to any one of Examples 145 to 152, wherein the lower layer includes a stack disposed on or across the substrate.

[0246]

[0249] Example 154. The workpiece and / or device according to Example 153, wherein the stack comprises alternating layers of silicon oxide and silicon nitride.

[0247]

[0250] Example 155. A workpiece and / or device comprising a lower layer disposed on a substrate, an alumina-carbon hybrid hard mask disposed on the lower layer, a silicon-containing hard mask disposed on the alumina-carbon hybrid hard mask, and a patterned photoresist (PR) layer disposed on the silicon-containing hard mask, wherein features extend through at least the alumina-carbon hybrid hard mask, the silicon-containing hard mask, and the patterned PR layer.

[0248]

[0251] Example 156. The workpiece and / or device according to Example 155, wherein the feature extends into at least a portion of the underlying layer.

[0249]

[0252] Example 157. The workpiece and / or device according to Example 155 or 156, wherein the alumina-carbon hybrid hard mask has a thickness of approximately 1 μm to approximately 20 μm.

[0250]

[0253] Example 158. A workpiece and / or device according to any one of Examples 155 to 157, wherein the features have a height of approximately 1 μm to approximately 20 μm.

[0251]

[0254] Example 159. A workpiece and / or device according to any one of Examples 155 to 158, wherein the features are separated by vias, gaps, or spaces having a width of approximately 5 nm to approximately 250 nm.

[0252]

[0255] Example 160. A workpiece and / or device according to any one of Examples 155 to 159, wherein the features have an aspect ratio of approximately 20 to approximately 500.

[0253]

[0256] Example 161. A workpiece and / or device according to any one of Examples 155 to 160, wherein the alumina-carbon hybrid hard mask contains approximately 5 at% to approximately 20 at% aluminum and approximately 5 at% to approximately 30 at% oxygen.

[0254]

[0257] Example 162. A workpiece and / or device according to any one of Examples 155 to 161, wherein the alumina-carbon hybrid hard mask further contains about 50 at% to about 90 at% carbon.

[0255]

[0258] Example 163. A workpiece and / or device according to any one of Examples 155 to 162, wherein the lower layer comprises a metal oxide, metal nitride, silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof.

[0256]

[0259] Example 164. A workpiece and / or device according to any one of Examples 155 to 163, wherein the lower layer includes a stack disposed on or across the substrate.

[0257]

[0260] Example 165. The workpiece and / or device according to Example 164, wherein the stack comprises alternating layers of silicon oxide and silicon nitride.

[0258]

[0261] Example 166. A workpiece and / or device comprising a metal or metal nitride layer disposed on a substrate, and an alumina-carbon hybrid hard mask disposed on the metal or metal nitride layer, wherein the alumina-carbon hybrid hard mask includes features.

[0259]

[0262] Example 167. The workpiece and / or device according to Example 166, wherein the alumina-carbon hybrid hard mask has a thickness of approximately 1 μm to approximately 20 μm.

[0260]

[0263] Example 168. The workpiece and / or device according to Example 166 or 167, wherein the alumina-carbon hybrid hard mask includes features having a height of approximately 1 μm to approximately 20 μm.

[0261]

[0264] Example 169. A workpiece and / or device according to any one of Examples 166 to 168, wherein the alumina-carbon hybrid hard mask includes features separated by vias, gaps, or spaces having a width of approximately 5 nm to approximately 250 nm.

[0262]

[0265] Example 170. A workpiece and / or device according to any one of Examples 166 to 169, wherein the features have an aspect ratio of approximately 20 to approximately 500.

[0263]

[0266] Example 171. A workpiece and / or device according to any one of Examples 166 to 170, wherein the alumina-carbon hybrid hard mask contains approximately 5 at% to approximately 20 at% aluminum and approximately 5 at% to approximately 30 at% oxygen.

[0264]

[0267] Example 172. A workpiece and / or device according to any one of Examples 166 to 171, wherein the alumina-carbon hybrid hard mask further contains about 50 at% to about 90 at% carbon.

[0265]

[0268] Example 173. A workpiece and / or device according to any one of Examples 166 to 172, wherein the metal or metallic nitride layer is a metallic layer, and the metallic layer comprises metallic titanium, metallic tantalum, metallic tungsten, an alloy thereof, or any combination thereof.

[0266]

[0269] Example 174. A workpiece and / or device according to any one of Examples 166 to 173, wherein the metal or metal nitride layer is a metal nitride layer, and the metal nitride layer comprises titanium nitride, tantalum nitride, tungsten nitride, an alloy thereof, or any combination thereof.

[0267]

[0270] Example 175. A workpiece and / or device comprising a metal or metal nitride layer disposed on a substrate, a silicon-containing hard mask disposed on the metal or metal nitride layer, and an alumina-carbon hybrid hard mask disposed on the silicon-containing hard mask and the metal or metal nitride layer, wherein the alumina-carbon hybrid hard mask includes features.

[0268]

[0271] Example 176. The workpiece and / or device according to Example 175, wherein the alumina-carbon hybrid hard mask has a thickness of approximately 1 μm to approximately 20 μm.

[0269]

[0272] Example 177. The workpiece and / or device according to Example 175 or 176, wherein the alumina-carbon hybrid hard mask includes features having a height of approximately 1 μm to approximately 20 μm.

[0270]

[0273] Example 178. A workpiece and / or device according to any one of Examples 175 to 177, wherein the alumina-carbon hybrid hard mask includes features separated by vias, gaps, or spaces having a width of approximately 5 nm to approximately 250 nm.

[0271]

[0274] Example 179. A workpiece and / or device according to any one of Examples 175 to 178, wherein the features have an aspect ratio of approximately 20 to approximately 500.

[0272]

[0275] Example 180. A workpiece and / or device according to any one of Examples 175 to 179, wherein the alumina-carbon hybrid hard mask contains approximately 5 at% to approximately 20 at% aluminum and approximately 5 at% to approximately 30 at% oxygen.

[0273]

[0276] Example 181. A workpiece and / or device according to any one of Examples 175-180, wherein the alumina-carbon hybrid hard mask further contains about 50 at% to about 90 at% carbon.

[0274]

[0277] Example 182. A workpiece and / or device according to any one of Examples 175 to 181, wherein the metal or metal nitride layer is a metal layer, and the metal layer comprises metallic titanium, metallic tantalum, metallic tungsten, an alloy thereof, or any combination thereof.

[0275]

[0278] Example 183. A workpiece and / or device according to any one of Examples 175 to 182, wherein the metal or metal nitride layer is a metal nitride layer, and the metal nitride layer comprises titanium nitride, tantalum nitride, tungsten nitride, an alloy thereof, or any combination thereof.

[0276]

[0279] Example 184. A workpiece and / or device according to any one of Examples 175 to 183, wherein the silicon-containing hard mask comprises silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof.

[0277]

[0280] Example 185. A workpiece and / or device according to any one of Examples 144 to 184, wherein the device is a memory device, a logic device, or a microelectronic device.

[0278]

[0281] While the above description applies to embodiments of the present disclosure, other embodiments and further embodiments may be devised without departing from the basic scope of the present disclosure, and the scope of the present disclosure is determined by the claims. All documents mentioned herein, including any prior documents and / or test procedures, are incorporated herein by reference, insofar as they do not conflict with the text of this specification. As is obvious from the above summary and specific embodiments, the forms of the present disclosure have been illustrated and described, but various modifications can be made without departing from the essence and scope of the present disclosure. Therefore, the present disclosure is not intended to be limited by the forms of the present disclosure. Similarly, the word “comprising” is considered synonymous with the word “including” in the interpretation of U.S. law. Similarly, whenever a composition, element, or group of elements is preceded by the transitional phrase “comprising,” it is assumed that the same group of compositions or elements has the transitional phrase “essentially consisting of,” “consisting of,” “selected from a group consisting of,” or “is,” followed by the enumeration of the composition, element, or group of elements, and vice versa. As used herein, the term "approximately" refers to a variation of + / - 10% from the nominal value. It should be understood that such variation may be present in any value provided herein.

[0279]

[0282] Some embodiments and features are described using sets of upper and lower numerical limits. Unless otherwise indicated, it should be understood that ranges are assumed to include any combination of any two values, for example, any combination of any lower value and any upper value, any combination of any two lower values, and / or any combination of any two upper values. One or more claims describe specific lower limits, upper limits, and ranges.

Claims

1. A method for forming a device, Positioning the workpiece within the process area of ​​the processing chamber, A carbon hard mask layer placed on or over the entire lower layer, A silicon-containing hard mask disposed on or throughout the carbon hard mask layer, and A patterned photoresist layer having a feature pattern is placed on the silicon-containing hard mask. This includes positioning the workpiece, Etching the silicon-containing hard mask and the carbon hard mask layer so that each has the feature pattern of the patterned photoresist layer, The carbon hard mask layer is treated by exposing the workpiece to a sequential infiltration synthesis (SIS) process to produce an alumina-carbon hybrid hard mask with a higher density than the carbon hard mask layer, and then, Etching the underlying layer to have the feature pattern of the patterned photoresist layer A method that includes this.

2. The SIS process comprises one or more infiltration cycles, and each of the infiltration cycles is Exposing the carbon hard mask layer to an aluminum precursor, The aluminum precursor is impregnated into the carbon hard mask layer through pores contained in the carbon hard mask layer, The process area is purged to remove the gaseous residue containing the aluminum precursor, Exposing the carbon hard mask layer to an oxidizing agent, The oxidizing agent is permeated into the carbon hard mask layer through the pores contained in the carbon hard mask layer to produce an alumina coating disposed on the inner surface of the carbon hard mask layer. Purging the process area to remove the gaseous residue containing the oxidizing agent. The method according to claim 1, including the method described in claim 1.

3. The method according to claim 2, wherein the aluminum precursor comprises an alkylaluminum compound, and the oxidizing agent comprises water, ozone, atomic oxygen, oxygen plasma, hydrogen peroxide, or any combination thereof.

4. The method according to claim 2, wherein the aluminum precursor comprises trimethylaluminum, the oxidizing agent comprises water, and the permeation cycle is repeated 2 to about 50 times during the SIS process.

5. During the SIS process, the process area of ​​the processing chamber is at a pressure of approximately 0.01 Torr to approximately 250 Torr. During each of the aforementioned penetration cycles, the carbon hard mask layer is exposed to the aluminum precursor for approximately 1 to 10 minutes, during which time the aluminum precursor is allowed to penetrate the carbon hard mask layer. During each of the aforementioned infiltration cycles, the carbon hard mask layer is exposed to a purge gas for approximately 1 to 30 minutes, during which time the process area is purged to remove the gaseous residue containing the aluminum precursor. During each of the aforementioned penetration cycles, the carbon hard mask layer is exposed to the oxidizing agent for approximately 1 to 10 minutes, during which time the oxidizing agent is allowed to penetrate the carbon hard mask layer. Between each of the aforementioned penetration cycles, the carbon hard mask layer is exposed to a purge gas for approximately 1 to 30 minutes, during which time the process area is purged to remove the gaseous residue containing the oxidizer. The method according to claim 2.

6. The method according to claim 1, wherein the patterned photoresist layer is produced by an extreme ultraviolet (EUV) lithography process or a deep ultraviolet (DUV) lithography process.

7. The method according to claim 1, wherein the device is a memory device, a logic device, or a microelectronic device, and the feature pattern is completely etched over the entire thickness of the silicon-containing hard mask.

8. Etching the silicon-containing hard mask further comprises exposing the silicon-containing hard mask to a fluorocarbon etching solution and a process gas, wherein the fluorocarbon etching solution comprises tetrafluoromethane, trifluoromethane, difluoromethane, monofluoromethane, octafluorocyclobutane, hexafluoro-1,3-butadiene, or any combination thereof, and the process gas comprises argon, helium, nitrogen (N ２ ), oxygen (O ２ The method according to claim 1, comprising, or any combination thereof.

9. The method according to claim 1, wherein the feature pattern is completely etched over the entire thickness of the carbon hard mask layer, and etching the carbon hard mask layer further comprises exposing the carbon hard mask layer to an etching gas and a passivation gas, wherein the etching gas comprises argon, oxygen, or a combination thereof, and the passivation gas comprises methane, sulfur dioxide, carbonyl sulfide, or any combination thereof.

10. The feature pattern is partially etched to the thickness of the underlying layer, and the partial etching of the underlying layer further comprises exposing the underlying layer to a carbon fluoride etching solution and a process gas, wherein the carbon fluoride etching solution includes tetrafluoromethane, trifluoromethane, difluoromethane, monofluoromethane, octafluorocyclobutane, hexafluoro-1,3-butadiene, or any combination thereof, and the process gas is argon, helium, nitrogen (N ２ ), oxygen (O ２ The method according to claim 1, comprising, or any combination thereof.

11. The method according to claim 1, wherein the carbon hard mask layer has a thickness of about 1 μm to about 20 μm.

12. The carbon hard mask layer is a patterned layer, The patterned layer includes features having a height of approximately 1 μm to approximately 20 μm. The patterned layer includes features separated by vias, gaps, or spaces having a width of approximately 5 nm to approximately 250 nm. The patterned layer includes features having aspect ratios of approximately 20 to approximately 500. The method according to claim 1.

13. The carbon hard mask layer comprises a carbon-containing material having polar functional groups, The alumina coating is placed on the inner surface having the polar functional group, The polar functional group includes a C-H group, a C-O group, a C=O group, or any combination thereof. The method according to claim 1.

14. The method according to claim 1, wherein the carbon hard mask layer is deposited by a thermochemical vapor deposition (CVD) process, a plasma-enhanced CVD (PE-CVD) process, a fluid CVD (FCD) process, or a spin-on process.

15. The method according to claim 1, wherein the carbon hard mask layer comprises about 30 atomic percent (at%) to about 80 at% carbon, about 10 at% to about 50 at% hydrogen, and about 10 at% to about 20 at% oxygen.

16. The method according to claim 1, wherein the alumina-carbon hybrid hard mask comprises about 5 at% to about 20 at% aluminum, about 5 at% to about 30 at% oxygen, and about 50 at% to about 90 at% carbon.

17. The method according to claim 1, wherein the lower layer comprises a metal oxide, a metal nitride, silicon oxide, silicon nitride, silicon oxynitride, dopants thereof, or any combination thereof.

18. The method according to claim 1, wherein the lower layer includes a stack disposed on or over the substrate, and the stack includes alternating layers of silicon oxide and silicon nitride.

19. A method for forming a device, Positioning the workpiece within the process area of ​​the processing chamber, A carbon hard mask layer placed on or over the entire lower layer, A silicon-containing hard mask disposed on or throughout the carbon hard mask layer, and A patterned photoresist layer having a feature pattern is placed on the silicon-containing hard mask. This includes positioning the workpiece, Etching the silicon-containing hard mask and the carbon hard mask layer so that each has the feature pattern of the patterned photoresist layer, The carbon hard mask layer is treated by exposing the workpiece to a sequential infiltration synthesis (SIS) process to produce an alumina-carbon hybrid hard mask with a density higher than that of the carbon hard mask layer, wherein the SIS process comprises one or more infiltration cycles, and each of the infiltration cycles is The carbon hard mask layer is exposed to an aluminum precursor for about 1 to 10 minutes, during which time the aluminum precursor is allowed to permeate the carbon hard mask layer through the pores contained in the carbon hard mask layer. The carbon hard mask layer is exposed to a purge gas for approximately 1 to 30 minutes, during which time the process area is purged to remove the gaseous residue containing the aluminum precursor. The carbon hard mask layer is exposed to an oxidizing agent for about 1 to 10 minutes, during which time the oxidizing agent is allowed to penetrate the carbon hard mask layer through the pores contained in the carbon hard mask layer, thereby generating an alumina coating disposed on the inner surface of the carbon hard mask layer, and The carbon hard mask layer is exposed to the purge gas for approximately 1 to 30 minutes, during which time the process area is purged to remove the gaseous residue containing the oxidizing agent. Processing the carbon hard mask layer, which includes, and then, Etching the underlying layer to have the feature pattern of the patterned photoresist layer A method that includes this.

20. The method according to claim 19, wherein the carbon hard mask layer comprises about 30 atomic percent (at%) to about 80 at% carbon, about 10 at% to about 50 at% hydrogen, and about 10 at% to about 20 at% oxygen.

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