# Patent

## Title
Methods of forming semiconductor device structures, and related semiconductor device structures

## Abstract

A method of forming a semiconductor device structure comprises forming a template material over a substrate, the template material exhibiting preferential wetting to a polymer block of a block copolymer. A positive tone photoresist material is formed over the template material. The positive tone photoresist material is exposed to radiation to form photoexposed regions and non-photoexposed regions of the positive tone photoresist material. The non-photoexposed regions of the positive tone photoresist material are removed with a negative tone developer to form a pattern of photoresist features. The pattern of photoresist features and unprotected portions of the template material are exposed to an oxidizing plasma to form trimmed photoresist features and a pattern of template features. The trimmed photoresist features are removed with a positive tone developer. Other methods of forming a semiconductor device structure, and a semiconductor device structure are also described.

## Background
TECHNICAL FIELD
Embodiments of the disclosure relate to the field of semiconductor device design and fabrication. More specifically, embodiments of the disclosure relate to methods of forming semiconductor device structures, and to related semiconductor device structures.
BACKGROUND
A continuing goal of integrated circuit fabrication is to decrease the dimensions thereof. Integrated circuit dimensions can be decreased by reducing the dimensions and spacing of the constituent features or structures thereof For example, by decreasing the dimensions and spacing of features (e.g., storage capacitors, access transistors, access lines) of a memory device, the overall dimensions of the memory device may be decreased while maintaining or increasing the storage capacity of the memory device.
Reducing the dimensions and spacing of semiconductor device features places ever increasing demands on the methods used to form the features. For example, due to limitations imposed by optics and radiation wavelengths, many conventional photolithographic methods cannot facilitate the formation of features having critical dimensions (e.g., widths, diameters) of less than about forty (40) nanometers (nm). Electron beam (E-beam) lithography and extreme ultraviolet (EUV) lithography have been used to form features having critical dimensions less than 40 nm, but generally require complex processes and significant costs.
One approach for achieving semiconductor device features having critical dimensions of less than about 40 nm has been patterning using chemical pattern-directed self-assembly (e.g., chemoepitaxy) of a block copolymer material, wherein a patterned template material is used to direct the self-assembly of a block copolymer material to form domains of a polymer block of a block copolymer distinct from domains of another polymer block of the block copolymer. A preferential wetting affinity of the patterned template material for one of the polymer blocks of the block copolymer directs the self-assembly of the distinct domains in accordance with the patterned template material. The domains of the polymer block or the domains of the another polymer block can be selectively removed, and the remaining domains can be utilized as desired (e.g., as an etch mask for patterning features into an underlying substrate or material). As the dimensions of the distinct domains are at least partially determined by the chain length of the block copolymer, feature dimensions much smaller than 40 nm are achievable (e.g., dimensions similar to those achievable through E-beam and EUV lithography processes).
Unfortunately, conventional methods of forming the patterned template material utilized for the chemical pattern directed self-assembly of the block copolymer material can suffer from a variety of problems. For instance, one conventional method includes foiniing a positive tone photoresist material over a template material, exposing the positive tone photoresist to radiation, removing photoexposed regions of the positive tone photoresist material with a positive tone developer to form a patterned photoresist material, removing portions of the patterned photoresist material and the template material using a plasma of oxygen (O2), chlorine (Cl2), and hydrogen (H2), and removing remaining portions of the patterned photoresist material using a negative tone developer. Such a method can be inefficient and cost-prohibitive due to the limited number of plasma and developer chemistries suitable for use with the method. For example, negative tone developers suitable for removing the patterned photoresist material generally include hazardous materials, such as dimethyl sulphoxide (DMSO), that necessitate the use of separate, specialized, and costly equipment and processes to mitigate health, safety, and environmental concerns, and equipment longevity concerns related to the use of such hazardous materials.
A need, therefore, exists for new, simple, and cost-efficient methods of forming semiconductor device structures and patterned template materials for use in chemical pattern directed self-assembly of block copolymer materials. It would be further desirable if the methods were compatible with a wide variety of conventional tools, processes, and materials.



BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIGS. 1A through 1F are partial cross-sectional views of a semiconductor device structure and illustrate a method of forming a semiconductor device structure including a patterned template material, in accordance with embodiments of the disclosure.



DETAILED DESCRIPTION
Methods of forming semiconductor device structures are disclosed, as are related semiconductor device structures. In some embodiments, a method of forming a semiconductor device structure includes forming a template material exhibiting preferential wetting to a polymer block of a block copolymer over a substrate. A photoresist material may be formed over the template material, and may be selectively exposed to radiation to form a photoexposed photoresist material including photoexposed regions and non-photoexposed regions. The non-photoexposed regions of the photoexposed photoresist material may be removed with a negative tone developer to form a patterned photoresist material including photoresist features separated by trenches. The patterned photoresist material and regions of the template material unprotected by (e.g., exposed through) the patterned photoresist material may be exposed to an oxidizing plasma to remove portions of the patterned photoresist material and the template material and form a patterned template material. Remaining portions of the patterned photoresist material may then be selectively removed using a positive tone developer. The methods disclosed herein may overcome problems associated with conventional methods of forming a patterned template material for use in chemical directed self-assembly of a block copolymer material, such as efficiency, cost, health, safety, and environmental problems related to conventional methods of forming such a patterned template material. Patterned template materials formed by the methods disclosed herein may exhibit feature dimensions equivalent to or better than feature dimensions of patterned template materials formed by conventional methods.
The following description provides specific details, such as material types, material thicknesses, and processing conditions in order to provide a thorough description of embodiments of the disclosure. However, a person of ordinary skill in the art will understand that the embodiments of the disclosure may be practiced without employing these specific details. Indeed, the embodiments of the disclosure may be practiced in conjunction with conventional fabrication techniques employed in the industry. In addition, the description provided below does not form a complete process flow for manufacturing a semiconductor device. The semiconductor device structures described below do not form a complete semiconductor device. Only those process acts and structures necessary to understand the embodiments of the disclosure are described in detail below. Additional acts to form the complete semiconductor device from the intermediate semiconductor device structures may be performed by conventional fabrication techniques. Also note, any drawings accompanying the application are for illustrative purposes only, and are thus not drawn to scale. Additionally, elements common between figures may retain the same numerical designation.
As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As used herein, relational teiris, such as “first,” “second,” “over,” “top,” “upper,” “bottom,” “underlying,” “lower,” etc., are used for clarity and convenience in understanding the disclosure and accompanying drawings and does not connote or depend on any specific preference, orientation, or order, except where the context clearly indicates otherwise.
As used herein, the term “substantially,” in reference to a given parameter, property, or condition, means to a degree that one of ordinary skill in the art would understand that the given parameter, property, or condition is met with a small degree of variance, such as within acceptable manufacturing tolerances.
FIGS. 1A through 1F, are simplified partial cross-sectional views illustrating embodiments of a method of forming a semiconductor device structure including a patterned template material, such as a patterned template material for use in the chemical-directed self-assembly of a block copolymer material. With the description provided below, it will be readily apparent to one of ordinary skill in the art that the methods described herein may be used in various devices. In other words, the methods of the disclosure may be used whenever it is desired to form a patterned template material over a substrate.
Referring to FIG. 1A, a semiconductor device structure 100 may include a substrate 102, and a template material 104. The template material 104 may be formed on or over the substrate 102. As used herein, the term “substrate” means and includes a base material or other construction upon which additional materials are formed. The substrate 102 may, for example, be a semiconductor substrate, a base semiconductor material on a supporting structure, a metal electrode, a semiconductor substrate having one or more materials, features, structures or regions formed thereon, another base material, or another construction. As a non-limiting example, the substrate 102 may be a conventional silicon substrate or other bulk substrate comprising a layer of semiconductive material. As used herein, the term “bulk substrate” means and includes not only silicon wafers, but also silicon-on-insulator (SOI) substrates, such as silicon-on-sapphire (SOS) substrates and silicon-on-glass (SOG) substrates, epitaxial layers of silicon on a base semiconductor foundation, and other semiconductor or optoelectronic materials, such as silicon-germanium, germanium, gallium arsenide, gallium nitride, and indium phosphide. The substrate 102 may be doped or undoped.
The template material 104 may be a material that, upon being patterned, facilitates forming a self-assembled block copolymer material. As used herein, the term “block copolymer material” means and includes a material formed of and including at least one block copolymer. In turn, as used herein, the term “block copolymer” means and includes a polymer including two or more polymer blocks bound to one or more polymer blocks of unlike (e.g., different) type. The template material 104 may, for example, be formed from a material that exhibits preferential wetting to one polymer block (e.g., a minority block, or a majority block) of a block copolymer. As used herein, the term “preferential wetting” refers to wetting of a contacting surface by a block copolymer wherein one polymer block of the block copolymer will wet the contacting surface at an interface with lower free energy than at least one other polymer block of the block copolymer. Thus, the different polymer blocks of the block copolymer may have different affinities for the contacting surface. Conversely, as used herein, the term “neutral wetting” refers to wetting of a contacting surface by a block copolymer wherein different polymer blocks of the block copolymer will wet the contacting surface at an interface with substantially the same free energy. Thus, the different polymer blocks may have equal or substantially equal affinity for the contacting surface. As a non-limiting example, the template material 104 may be formed of and include at least one material (e.g., a polystyrene-containing material) formulated to be preferential wetting to a polystyrene (PS) block of a block copolymer. In some embodiments, the template material 104 is formed of and includes a material preferential wetting toward a PS block of poly(styrene-b-methylmethacrylate) (PS-b-PMMA). In additional embodiments, the template material 104 is formulated to be preferential wetting toward a PS block of poly(styrene-block-dimethylsiloxane) (PS-b-PDMS).
The template material 104 may have any thickness T1 conducive to removing (e.g., etching) desired regions of the template material 104 to form a patterned template material, as described in further detail below. By way of non-limiting example, the thickness T1 of the template material 104 may be greater than or equal to about 5 nanometers (nm), such as within a range of from about 5 nm to about 15 nm, within a range of from about 8 nm to about 12 nm, or within a range of from about 8 nm to about 10 nm. In some embodiments, the thickness T1 of the template material 104 is about 10 nm.
Each of the substrate 102, and the template material 104 may be formed using conventional processes including, but not limited to, physical vapor deposition (“PVD”), chemical vapor deposition (“CVD”), atomic layer deposition (“ALD”), or spin-coating. PVD includes, but is not limited to, sputtering, evaporation, or ionized PVD. Such processes are known in the art and, therefore, are not described in detail herein.
Referring to FIG. 1B, a photoresist material 106 may be formed on or over the template material 104. The photoresist material 106 may be a positive tone photoresist material, such as a positive tone photoresist material formulated to be more effectively developed by a negative tone developer than a positive tone developer. Suitable positive tone photoresist materials are known in the art, and are, therefore, not described in detail herein. For example, the photoresist material 106 may include at least one polymer including a repeating unit exhibiting at least one acid-decomposable group formulated to hydrolyze upon reaction with an acid, and at least one acid generator (e.g., a photoacid generator, a thermal acid generator). The photoresist material 106 may be formulated such that regions of the photoresist material 106 exposed to radiation (e.g., ultraviolet radiation) and a post-exposure bake become substantially soluble in a positive tone developer and substantially insoluble in a negative tone developer. As used herein, the term “positive tone developer” refers to a material, such as an aqueous alkaline solution (e.g., aqueous tetramethylammonium hydroxide (TMAH)), by which portions of the positive tone photoresist material exposed to radiation are at least partially dissolved and removed. Conversely, as used herein, the term “negative tone developer” refers to a material, such as an organic solvent (e.g., n-butyl acetate), by which portions of the positive tone photoresist material not exposed to radiation are at least partially dissolved and removed. The radiation may substantially increase the polarity of photoexposed regions of the photoresist material 106 relative to that of non-photoexposed regions of the photoresist material 106. Accordingly, the non-photoexposed regions of the photoresist material 106 may be substantially completely removed by the negative tone developer while the photoexposed regions may remain substantially intact (e.g., not removed), as described in further detail below. The formulation of photoresist material 106 may be compatible with 193 nanometer (nm) and 248 nm photolithography systems.
The photoresist material 106 may have any thickness T2 conducive to forming photoresist features that may be used to form a patterned template material from the template material 104, as described in further detail below. By way of non-limiting example, the thickness T2 of the photoresist material 106 may be greater than or equal to about 15 nm, such as within a range of from about 20 nm to about 150 nm, within a range of from about 50 nm to about 120 nm, or within a range of from about 70 nm to about 110 nm. In some embodiments, the thickness T2 of the photoresist material 106 is about 90 nm.
The photoresist material 106 may be formed on or over the template material 104 using conventional processes (e.g., a conventional deposition process, a conventional baking process) and equipment, which are not described in detail herein.
Referring to FIG. 1C, the photoresist material 106 (FIG. 1B) may be selectively exposed to radiation 112 (e.g., a wavelength of ultraviolet radiation less than or equal to 248 nm, such as a 193 nm wavelength of ultraviolet radiation) to form a photoexposed photoresist material 108 including photoexposed regions 108a and non-photoexposed regions 108b. The photoexposed regions 108a may be separated from one another by the non-photoexposed regions 108b. As shown in FIG. 1C, the photoresist material 106 (FIG. 1B) may be exposed to the ultraviolet radiation 112 through a mask 110 including a predetermined pattern to form the photoexposed regions 108a and non-photoexposed regions 108b. In additional embodiments, the photoexposed photoresist material 108 may be formed through direct writing (e.g., without a mask) of the photoresist material 106. The photoexposed regions 108a of the photoexposed photoresist material 108 may be substantially more soluble in a positive tone developer (e.g., an aqueous 2.38% TMAH solution) than the non-photoexposed regions 108b of photoexposed photoresist material 108, and the non-photoexposed regions 108b of the photoexposed photoresist material 108 may be substantially more soluble in a negative tone developer (e.g., n-butyl acetate) than the photoexposed regions 108a of the photoexposed photoresist material 108. In some embodiments, the photoexposed regions 108a of the photoexposed photoresist material 108 are substantially soluble in the positive tone developer and substantially insoluble in the negative tone developer, and the non-photoexposed regions 108b of photoexposed photoresist material 108 are substantially soluble in the negative tone developer and substantially insoluble in the positive tone developer. A conventional post-exposure bake may be utilized to enhance the solubility of the photoexposed regions 108a in the positive tone developer.
The photoexposed regions 108a and the non-photoexposed regions 108b (and, hence, the configuration of the mask 110) may be configured to exhibit any desired dimensions and spacing. The dimensions and spacing of the photoexposed regions 108a may be selected at least partially based on desired dimensions and spacing of template features to be formed using a patterned photoresist material formed from the photoexposed photoresist material 108, as described in further detail below. Each of the photoexposed regions 108a (and, hence, each of the non-photoexposed regions 108b) may be configured to exhibit substantially the same dimensions and spacing, or at least one of the photoexposed regions 108a may exhibit at least one of different dimensions and different spacing than at least one other of the photoexposed regions 108a. In some embodiments, each of the photoexposed regions 108a is configured to exhibit substantially the same dimensions and spacing. For example, the photoexposed regions 108a may each be configured to exhibit substantially the same thickness T2 (e.g., that of the photoresist material 106 previously described in relation to FIG. 1B), length (not shown), and substantially the same width W1. The width W1 of each of the photoexposed regions 108a may, for example, be less than or equal to about 80 nm, such as within a range of from about 30 nm to about 80 nm, within a range of from about 40 nm to about 70 nm, or within a range of from about 50 nm to about 60 nm. In some embodiments, the width W1 of each of the photoexposed regions 108a is about 55 nm. In addition, the photoexposed photoresist material 108 may be formed to exhibit substantially the same pitch P1 between adjacent photoexposed regions 108a. As used herein, the term “pitch” refers to the distance between identical points in two adjacent (i.e., neighboring) features. The pitch P1 between the adjacent photoexposed regions 108a may, for example, be characterized as the distance between centers of the adjacent photoexposed regions 108a. In some embodiments, the pitch P1 between adjacent photoexposed regions 108a is about 128 nm.
Referring next to FIG. 1D, the photoexposed photoresist material 108 (FIG. 1C) may be exposed to a negative tone developer to selectively remove the non-photoexposed regions 108b (FIG. 1C) and form a patterned photoresist material 114 including photoresist features 114a separated by trenches 115. As depicted in FIG. 1D, the trenches 115 may be defined by opposing sidewalls of adjacent photoresist features 114a, and by an exposed upper surface of the template material 104. The photoresist features 114a may correspond to the photoexposed regions 108a of the photoexposed photoresist material 108. Accordingly, the photoresist features 114a may be substantially soluble in a positive tone developer (e.g., an aqueous alkaline solution), and may exhibit substantially the same dimensions and spacing as the photoexposed regions 108a of the photoexposed photoresist material 108.
The negative tone developer used to pattern the photoresist material 106 (FIG. 1B) may be any developer formulated to substantially completely remove the non-photoexposed regions 108b of the photoexposed photoresist material 108 without substantially removing the photoexposed regions 108a of the photoexposed photoresist material 108. By way of non-limiting example, the negative tone developer may be a developer including at least one organic solvent, such as at least one of a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, an ether-based solvent, and a hydrocarbon-based solvent. Suitable ketone-based solvents include, but are not limited to, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, actonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate. Suitable ester-based solvents include, but are not limited to, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, ethyl-3-ethoxypropionate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate. Suitable alcohol-based solvents include, but are not limited to, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, and n-decanol; a glycol-based solvent such as ethylene glycol, diethylene glycol, and triethylene glycol; and a glycol ether-based solvent such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxy methyl butanol. Suitable amide-based solvents include, but are not limited to, hexamethylphosphoric triamide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and 1,3-dimethyl-2-imidazolidinone. Suitable ether-based solvents include, but are not limited to, the glycol ether-based solvents previously described, dioxane, and tetrahydrofuran. Suitable hydrocarbon-based solvents include, but are not limited to, aromatic hydrocarbon-based solvents, such as toluene and xylene; and aliphatic hydrocarbon-based solvents, such as pentane, hexane, octane, and decane. The negative tone developer may be selected at least partially based on the material composition of the photoresist material 106 (FIG. 1B). In some embodiments, the negative tone developer comprises neat (e.g., undiluted) n-butyl acetate. The photoexposed photoresist material 108 may be exposed to the negative tone developer using conventional processes and equipment, which are not described in detail herein.
Removing portions of the photoexposed photoresist material 108 (FIG. 1C) using a negative tone developer (e.g., n-butyl acetate) may reduce the complexity and costs of forming a patterned template material, increase production efficiency, and mitigate health, safety, and environmental concerns as compared to conventional methods utilizing a positive tone developer (e.g., an aqueous alkaline solution). For example, as described in further detail below, using a negative tone developer to form the patterned photoresist material 114 may enable a broader range of etch chemistries to be used, and may also enable the use of relatively less toxic materials (e.g., developers) to remove photoresist features remaining following the formation of the patterned template material.
Referring next to FIG. 1E, the patterned photoresist material 114 (FIG. 1D) and unprotected (e.g., exposed) portions of the template material 104 (FIG. 1D) may be exposed to an oxidizing plasma to forni a patterned template material 116 including template features 116a separated by trenches 120. The oxidizing plasma may remove (e.g., etch) portions of the photoresist features 114a to faun trimmed photoresist features 118a and may simultaneously remove (e.g., etch) the unprotected portions of the template material 104 to form the template features 116a. As the oxidizing plasma reduces (e.g., trims) lateral dimensions of the photoresist features 114a, the unprotected portions of the template material 104 may increase in size, enabling additional amounts of the template material 104 to be removed. The use of the oxidizing plasma may enable relatively large portions of the patterned photoresist material 114 to be removed with underlying portions of the template material 104 to simultaneously form the trimmed photoresist features 118a and the template features 116a. By way of example, the oxidizing plasma may remove greater than or equal to about 20 nm of the patterned photoresist material 114, such as greater than or equal to about 30 nm of the patterned photoresist material 114, or greater than or equal to about 40 nm of the patterned photoresist material 114. In some embodiments, the oxidizing plasma removes about 40 nm of the patterned photoresist material 114.
The oxidizing plasma may be any oxygen-containing plasma formulated to remove exposed portions of the patterned photoresist material 114 and the template material 104 while enabling the trimmed photoresist features 118a ultimately formed to at least exhibit a solubility in a positive tone developer (e.g., an aqueous alkaline solution) substantially similar to the solubility of the photoresist features 114a (FIG. 1D) in the positive tone developer. In some embodiments, use of the oxidizing plasma may enhance the solubility of the trimmed photoresist features 118a in a positive tone developer relative to that of the photoresist features 114a. For example, the oxidizing plasma may volatilize and remove portions of the photoresist features 114a to form the trimmed photoresist features 118a (as well as volatilizing and removing unprotected portions of the template material 104 to form the template features 116a), and may also oxidize surfaces of the trimmed photoresist features 118a so that the trimmed photoresist features 118a are more soluble in a positive tone developer as compared to the photoresist features 114a. Put another way, the oxidizing plasma may increase the polarity of the trimmed photoresist features 118a relative to the photoresist features 114a. In some embodiments, the oxidizing plasma converts (e.g., oxidizes) ester groups in the photoresist material 114 to carboxylic acid groups, which increases the polarity and, thus, solubility of the trimmed photoresist features 118a in a positive tone developer (e.g., an aqueous alkaline solution). The oxidizing plasma may include, for example, at least one oxidizing agent (e.g., oxygen, sulfur dioxide, nitrogen dioxide, nitrous oxide, dinitrogen tetroxide), and at least one noble gas element (e.g., helium, neon, argon, krypton, xenon, radon). The oxidizing plasma may be substantially free of materials that would otherwise reduce the solubility of the trimmed photoresist features 118a in the positive tone developer. The oxidizing plasma may, for example, be substantially free of fluorine (F) atoms, chlorine (Cl) atoms, and bromine (Br) atoms. By way of non-limiting example, the oxidizing plasma may be substantially free of nitrogen triflouride (NF3), diflouromethane (CH2F2), carbon tetraflouride (CF4), sulfur hexaflouride (SF6), Cl2, and hydrogen bromide (HBr). In some embodiments, the oxidizing plasma is substantially free of materials other than the oxidizing agent and the noble gas element. By way of non limiting example, the oxidizing plasma may comprise a plasma of oxygen (O2) and helium (He), a plasma of sulfur dioxide (SO2) and He, or a plasma of O2, SO2, and He. In some embodiments, the oxidizing plasma is a plasma of O2 and He. In additional embodiments, the oxidizing plasma is substantially free of materials other than the oxidizing agent. For example, in some embodiments, the oxidizing plasma is an O2 plasma.
The relative amounts of the various components (e.g., the oxidizing agent, the noble gas element) of the oxidizing plasma may be selected based on the dimensions and material compositions of the template material 104 (FIG. 1D) and the patterned photoresist material 114 (FIG. 1D), and based on desired dimensions of the template features 116a of the patterned template material 116. For example, the relative amounts of the various components of the oxidizing plasma may be selected to enable sufficient amounts of the photoresist features 114a and the template material 104 to be simultaneously removed to impart the template features 116a with desired dimensions. The oxidizing plasma may be more selective to one of the patterned template material 116 and the template material 104 than the other of the patterned template material 116 and the template material 104. As a non-limiting example, depending on the material compositions and relative dimensions of the photoresist features 114a and the template material 104, the oxidizing agent (e.g., O2) may comprise greater than or equal to about 10 percent of a total volume of the oxidizing plasma, such as greater than or equal to about 15 percent of the total volume of the oxidizing plasma, greater than or equal to about 20 percent of the total volume of the oxidizing plasma, greater than or equal to about 30 percent of the total volume of the oxidizing plasma, greater than or equal to about 40 percent of the total volume of the oxidizing plasma, or greater than or equal to about 50 percent of the total volume of the oxidizing plasma. The other components (e.g., He) may comprise the remainder of the oxidizing plasma. In some embodiments, O2 is provided into a chamber configured to generate the oxidizing plasma at a flow rate of about 15 standard cubic centimeters per minute (sccm), and He is provided into the chamber at a flow of about 68 sccm. Conditions, such as temperature and pressure, for generating and maintaining the oxidizing plasma may be conventional and, therefore, are not described in detail herein.
Exposure to the oxidizing plasma may continue until the template features 116a of the patterned template material 116 each exhibit a desired width W2. The width W2 may be selected based on one or more desired properties of a self-assembled block copolymer material (not shown) to be formed using the pattered template material 116 (e.g., through a conventional chemical pattern directed self-assembly process). The width W2 may, for example, be selected to be substantially the same as a width of at least one polymer domain of the self-assembled block copolymer material to be formed. The width of the polymer domain may be at least partially determined by the chain length of a block copolymer utilized to form the self-assembled block copolymer material. By way of non-limiting example, the width W2 of each of the template features 116a may be less than or equal to about 30 nm, such as less than or equal to about 20 nm, less than or equal to about 15 nm, or less than or equal to about 10 nm. In some embodiments, the width W2 of each of the template features 116a is about 15 nm. The template features 116a may each exhibit substantially the same thickness T1 as the template material 104 (FIG. 1D), and a pitch P2 between adjacent template features 116a of the patterned template material 116 may be substantially the same as the pitch P1 between the adjacent photoresist features 114a of the patterned photoresist 114 (FIG. 1D).
Referring to FIG. 1F, following the formation of the patterned template material 116, the semiconductor device structure 100 may be exposed to a positive tone developer to selectively remove the trimmed photoresist features 118a. The positive tone developer may be any developer formulated to substantially completely remove the trimmed photoresist features 118a without substantially removing the template features 116a of the patterned template material 116. By way of non-limiting example, the positive tone developer may be an aqueous alkaline solution, such as an aqueous solution of a quaternary ammonium salt (e.g., TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide), primary amines (e.g., ethylamine, n-propylamine), secondary amines (e.g., diethylamine, di-n-propylamine), tertiary amines (e.g., triethylamine), alcoholamines (e.g., triethanolamine), inorganic alkalis (e.g., potassium hydroxide, sodium hydroxide, ammonia water), and combinations thereof. The aqueous alkaline solution may include from about 1% by weight to about 5% by weight of the quaternary ammonium salt, primary amine, secondary amine, tertiary amine, alcoholamine, or inorganic alkali. Optionally, the positive tone developer may also include at least one additive, such as at least one of a surfactant, an antifoam agent, and a salt. In some embodiments, the positive tone developer is an aqueous 2.38% TMAH solution.
Advantageously, the positive tone developer used to remove the trimmed photoresist features 118a may be substantially free of many hazardous materials associated with conventional methods of removing positive tone photoresist features remaining after the formation of a patterned template material. As previously described, conventional methods of removing remaining positive tone photoresist features may require using at least one of a very limited number of suitable negative tone developers including hazardous solvents (e.g., DMSO). Such conventional methods may require complex, costly, and separate equipment to mitigate health, safety, and environmental concerns, and to prevent damage to other equipment utilized to form the patterned template material. In contrast, the method of the disclosure enables the trimmed photoresist features 118a to be removed using a relatively wide variety of less hazardous materials (e.g., materials not including organic solvents such as DMSO), which may not require the use of the complex, costly, and separate equipment needed for conventional methods.
Thus, in accordance with embodiments of the disclosure, a method of forming a semiconductor device structure comprises forming a template material over a substrate, the template material preferential wetting to a polymer block of a block copolymer. A positive tone photoresist material is formed over the template material. The positive tone photoresist material is exposed to radiation to form photoexposed regions and non-photoexposed regions of the positive tone photoresist material. The non-photoexposed regions of the positive tone photoresist material are removed with a negative tone developer to form a pattern of photoresist features. The pattern of photoresist features and unprotected portions of the template material are exposed to an oxidizing plasma to form trimmed photoresist features and a pattern of template features. The trimmed photoresist features are removed with a positive tone developer.
Furthermore, in accordance with additional embodiments of the disclosure, a method of forming a semiconductor device structure comprises forming a positive tone resist material over a template material over a substrate, the positive tone resist material formulated for negative tone development. The positive tone resist material is exposed to radiation having a wavelength of 193 nanometers to form a photoexposed photoresist material. The non-photoexposed regions of the photoexposed photoresist material are removed with a negative tone developer comprising an organic solvent to form a patterned photoresist material. The patterned photoresist material and the template material are exposed to a plasma consisting essentially of at least one oxidizing agent and at least one noble gas element to pattern the template material. Remaining portions of the patterned photoresist material are removed after patterning the template material.
In addition, a semiconductor device structure of an embodiment of the disclosure comprises a patterned template material over a substrate, the patterned template material formed by the method comprising forming a template material preferential wetting to a polymer block of a block copolymer over the substrate, forming a positive tone photoresist material formulated for negative tone development over the template material, exposing the positive tone photoresist material to radiation to form photoexposed regions of the positive tone photoresist material separated by non-photoexposed regions of the positive tone photoresist material, removing the non-photoexposed regions of the positive tone photoresist material to form a patterned photoresist material comprising photoresist features, exposing the photoresist features and unprotected portions of the template material to an oxidizing plasma to simultaneously form trimmed photoresist features and a patterned template material, and removing the trimmed photoresist features with an aqueous alkaline solution.
Following the removal of the trimmed photoresist features 118a, the semiconductor device structure 100 may be subjected to additional processing. For example, a neutral wetting material (not shown) may be formed within the trenches 120 between the template features 116a of the patterned template material 116, and a block copolymer material (not shown) may be formed on the template features 116a and the neutral wetting material. The block copolymer material may be self-assembled (e.g., by annealing) to form a self-assembled block copolymer material (not shown) including domains of at least one polymer block substantially aligned with the template features 116a of the patterned template material 116. Other domains of the self-assembled block copolymer material (e.g., domains of at least one other polymer block) may be selectively removed to form a polymeric pattern (not shown) including polymer features separated by additional trenches, the polymer features corresponding to the domains of the at least one polymer block. A pitch between adjacent polymer features of the polymeric pattern may be less than the pitch P2 between adjacent template features 116a of the patterned template material 116. Such additional processing may be performed using conventional processes and equipment, which are not described in detail herein.
The methods of the disclosure may advantageously mitigate health, safety, and environmental concerns, reduce costs, and increase production efficiency as compared to conventional methods of foiming a semiconductor device structure including a patterned template material for use in chemical pattern directed self-assembly of a block copolymer material, such as conventional methods utilizing a positive tone developer to foini a patterned photoresist material, and a negative tone developer to remove portions of the patterned photoresist material remaining after the formation the pattered template material. In addition, patterned template materials formed by the methods of the disclosure may exhibit feature dimensions (e.g., thicknesses, widths) at least equivalent to those of patterned template materials formed by conventional methods.
While the disclosure is susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and have been described in detail herein. However, the disclosure is not limited to the particular forms disclosed. Rather, the disclosure is to cover all modifications, equivalents, and alternatives falling within the scope of the disclosure as defined by the following appended claims and their legal equivalents.

## Claims

1. A method of forming a semiconductor device structure, comprising:
forming a positive tone photoresist material over a template material on a substrate, the template material exhibiting preferential wetting to polymer block a block copolymer;
exposing the positive tone photoresist material to radiation to form photoexposed regions and non-photoexposed regions of the positive tone photoresist material;
removing the non-photoexposed regions of the positive tone photoresist material with a negative tone developer to form a pattern of photoexposed photoresist features;
exposing the pattern of photoexposed photoresist features and unprotected portions of the template material to an oxidizing plasma consisting essentially of helium and at least one oxidizing agent to form trimmed, photoexposed photoresist features and a pattern of template features; and
removing the trimmed, photoexposed photoresist features with a positive tone developer.

2. The method of claim 1, wherein the template material comprises a material preferential wetting to a polystyrene block of a block copolymer.

3. The method of claim 1, wherein forming a positive tone photoresist material over a template material comprises forming the positive tone photoresist material over a template material having a thickness within a range of from about 5 nanometers to about 15 nanometers.

4. The method of claim 1, wherein forming a positive tone photoresist material comprises forming the positive tone photoresist material to a thickness within a range of from about 50 nanometers to about 100 nanometers.

5. The method of claim 1, wherein exposing the positive tone photoresist material to radiation to form photoexposed regions and non-photoexposed regions comprises forming the photoexposed regions to be substantially soluble in a positive tone developer and substantially insoluble in a negative tone developer.

6. The method of claim 1, wherein exposing the positive tone photoresist material to radiation to form photoexposed regions and non-photoexposed regions comprises forming each of the photoexposed regions to exhibit substantially the same dimensions.

7. The method of claim 1, wherein exposing the positive tone photoresist material to radiation to form photoexposed regions and non-photoexposed regions comprises forming each of the photoexposed regions to a width within a range of from about 30 nanometers to about 70 nanometers.

8. The method of claim 1, wherein removing the non-photoexposed regions of the positive tone photoresist material with a negative tone developer comprises removing the non-photoexposed regions with at least one of a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, an ether-based solvent, and a hydrocarbon-based solvent.

9. The method of claim 1, wherein removing the non-photoexposed regions of the positive tone photoresist material with a negative tone developer to form a pattern of photoexposed photoresist features comprises forming each of the photoresist features to exhibit substantially the same dimensions and spacing as the photoexposed regions of the positive tone photoresist material.

10. The method of claim 1, wherein exposing the pattern of photoresist features and unprotected portions of the template material to an oxidizing plasma comprises exposing the pattern of photoexposed photoresist features and the unprotected portions of the template material to a plasma that increases a solubility of the trimmed, photoexposed photoresist features in a positive tone developer relative to a solubility of the photoexposed photoresist features in the positive tone developer.

11. The method of claim 1 wherein expncing the pattern of photoexposed photoresist features and unprotected portions of the template material to an oxidizing plasma to form trimmed, photoexposed photoresist features and a pattern of template features comprises forming each of the template features to a width less than or equal to about 15 nanometers.

12. The method of claim 1, wherein removing the trimmed, photoexposed photoresist features with a positive tone developer comprises removing the trimmed, photoexposed photoresist features with an aqueous alkaline solution.

13. The method of claim 1, wherein removing the trimmed, photoexposed photoresist features with a positive tone developer comprises removing the trimmed, photoexposed photoresist features with an aqueous alkaline solution comprising from about 1% by weight to about 5% by weight of one or more of a quaternary ammonium salt, a primary amine, a secondary amine, a tertiary amine, an alcoholamine, and an inorganic alkali.

14. The method of claim 1, further comprising:
forming a neutral wetting material within trenches between template features of the pattern of template features;
forming the block copolymer on the template features and the neutral wetting material; and
annealing the block copolymer to form a self-assembled block copolymer comprising domains of the polymer block substantially aligned with the template features.

15. A method of forming a semiconductor device structure, comprising:
forming a positive tone resist material over a template material over a substrate, the positive tone resist material formulated for negative tone development;
exposing the positive tone resist material to radiation having a wavelength of 193 nanometers to form a photoexposed photoresist material;
removing non-photoexposed regions of the photoexposed photoresist material with a negative tone developer comprising an organic solvent to form a patterned photoresist material;
exposing the patterned photoresist material and the template material to an oxidizing plasma selected from the group consisting of a plasma of oxygen and helium, a plasma of sulfur dioxide and helium, and a plasma of oxygen, sulfur dioxide, and helium to pattern the template material; and
removing remaining portions of the patterned photoresist material after patterning the template material.

16. The method of claim 15, wherein removing non-photoexposed regions of the photoexposed photoresist material comprises selectively removing the non-photoexposed regions of the photoexposed photoresist material with n-butyl acetate.

17. The method of claim 15, wherein exposing the patterned photoresist material and the template material to an oxidizing plasma comprises selecting the oxidizing, plasma to consist essentially of oxygen and helium.

18. The method of claim 15, wherein removing remaining portions of the patterned photoresist material comprises removing the remaining portions of the patterned photoresist material with an aqueous 2.38 percent tetramethylammonium hydroxide solution.

19. The method of claim 15, wherein removing remaining portions of the patterned photoresist material comprises exposing the remaining portions of the patterned photoresist material to a positive tone developer.