Developer composition containing metal photoresist and pattern forming method including developing method using composition

Abstract

The invention provides a developer composition for a metal-containing photoresist and a pattern forming method including a developing method using the developer composition. For the coordinate x, as specified by Korean solubility parameters ([delta] d, [delta] p, and [delta] h) of the developer composition, a solubility radius Ra with the coordinate a as a central value can be calculated, and a solubility radius Rb with the coordinate b as a central value can be calculated. And the distance () between the coordinate x and the coordinate a and the distance () between the coordinate x and the coordinate b, respectively, calculated by Equation 1 and Equation 2, may have a relationship lt; ra and gt; rb. Equation 1 = 4 ([delta] dx-[delta] da) 2 + ([delta] px-[delta] da) 2 + ([delta] hx-[delta] ha) 2 = 4 ([delta] dx-[delta] db) 2 + ([delta] px-[delta] pb) 2 + ([delta] hx-[delta] hb) 2

Description

[0001] Cross-reference of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0134186, filed on October 2, 2024, with the Korean Intellectual Property Office, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] The present invention relates to a developer composition for a metal photoresist and a method for forming or providing a pattern, including a development method using the developer composition. Background Technology

[0004] The semiconductor industry has experienced a continuous reduction in critical dimensions, and for this reduction in dimensions, there is a desire to develop new types or kinds of high-performance photoresist materials and patterning methods suitable for processing and patterning increasingly smaller features.

[0005] Chemically amplified (CA) photoresists are designed to ensure high sensitivity, but their elemental composition (e.g., smaller amounts of oxygen (O), fluorine (F), sulfur (S), and / or carbon (C)) reduces absorbance at approximately 13.5 nm wavelengths, thus decreasing sensitivity. These photoresists may also experience additional difficulties under extreme ultraviolet (EUV) exposure. Furthermore, CA photoresists can be challenging due to roughness issues in small feature sizes, and line edge roughness (LER) experiments have shown to increase with decreasing photosensitivity, partly due to the nature of acid catalyst processes. Because of these drawbacks and problems with CA photoresists, the semiconductor industry needs or expects new types or varieties of high-performance photoresists.

[0006] For example, it is necessary or desirable to develop photoresists that ensure excellent or suitable etch resistance and resolution while (e.g., simultaneously) improving or enhancing sensitivity and enhancing critical dimension (CD) uniformity and LER properties in lithography processes. Summary of the Invention

[0007] One or more aspects of the embodiments of this disclosure relate to developer compositions for use with metal-containing photoresists.

[0008] One or more aspects of the embodiments of this disclosure relate to methods for forming or providing patterns, including a developing method using a developing agent composition.

[0009] Additional aspects of the embodiments will be set forth in part in the description which follows, and in part will be apparent from the description or may be learned by practice of the embodiments presented in this disclosure.

[0010] According to one or more embodiments, the developer composition applied to metal-containing photoresist includes,

[0011] Coordinate a, which is determined by 9 mJ / cm 2 Up to 12 mJ / cm 2 The first exposure energy is specified by the Hansen solubility parameters (δd, δp, and δh) of the first photoresist containing the metal photoresist.

[0012] Coordinate b, which has an energy 5 mJ / cm² higher than the first exposure. 2 Up to 10 mJ / cm 2 The second exposure energy is specified by the Hansen solubility parameters (δd, δp, and δh) of the second photoresist containing the metal photoresist; and

[0013] For coordinate x, specified by the Hansen solubility parameters (δd, δp, and δh) of the developer composition,

[0014] Calculate the solubility radius R with coordinate a as the center value. a ,

[0015] Calculate the solubility radius R with coordinate b as the center value (e.g., another center value). b ,and

[0016] The distance between coordinates x and a calculated by Equation 1 and Equation 2 respectively. ) and the distance between coordinates x and b ( ) have a relationship < Ra and > Rb.

[0017] Equation 1

[0018] = 4(δd x - δd a ) 2 + (δp x - δp a ) 2 + (δh x - δh a ) 2

[0019] Equation 2

[0020] = 4(δd x - δd b ) 2 + (δp x - δpb ) 2 + (δh x - δh b ) 2

[0021] Hansen solubility parameter (HSP), solubility radius R a and solubility radius R b Prediction can be made using the Generate Hansen Parameters module in the COSMOquick version 22 program.

[0022] A method for forming or providing a pattern according to one or more embodiments includes coating a metal-containing photoresist composition on a substrate, performing a heat treatment wherein a metal-containing photoresist film is formed or provided on the substrate by drying and heating, exposing the metal-containing photoresist film, and developing it using a developer composition for the metal-containing photoresist.

[0023] According to one or more embodiments, the developer composition applied to metal-containing photoresist may be a developer composition having specific (e.g., set or predetermined) Hansen solubility parameters derived through simulation. By applying a developer composition that satisfies the elements described in one or more embodiments, the solubility of the unexposed portion may be increased or enhanced, and the solubility of the exposed portion may be decreased, thereby improving or enhancing the contrast in solubility between the unexposed and exposed portions. This enables the realization of photoresist patterns in which the occurrence of scum and bridging is significantly reduced while maintaining excellent or suitable sensitivity. Attached Figure Description

[0024] The above and other aspects and features of specific embodiments of this disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings.

[0025] Figures 1A-1C A cross-sectional view is provided to illustrate the process steps in order to describe the method of forming or providing a pattern.

[0026] Figure 2 This is a schematic diagram illustrating the solubility range of each photoresist according to exposure energy by performing simulations on compositions according to one or more embodiments of this disclosure.

[0027] Explanation of icon numbers

[0028] 110: Feature layer;

[0029] 110P: Feature pattern;

[0030] 130P: Photoresist pattern;

[0031] OP: Opening;

[0032] Ra, Rb: solubility radii. Detailed Implementation

[0033] The subject matter of this disclosure will be described in more detail below with reference to the accompanying drawings. In the following description of this disclosure, functions or structures commonly understood by those skilled in the art may not be described in order to clarify the disclosure.

[0034] In describing embodiments of this disclosure, the word "may" refers to "one or more embodiments of this disclosure".

[0035] In this document, unless the context explicitly indicates otherwise, the singular forms “a / an” and “the” are intended to include the plural forms as well. Unless the context explicitly indicates otherwise, singular expressions include plural expressions.

[0036] As used herein, the terms “and / or” or “or” include any and all combinations of one or more of the associated enumerated items.

[0037] In this disclosure, expressions preceding a list of elements, such as “at least one,” “one of,” and “selected from,” modify the entire list of elements without modifying any individual elements of the list. For example, “at least one of a, b, or c,” “selected from at least one of a, b, and c,” “selected from at least one of a to c,” and / or similar expressions indicate only a, only b, only c, both a and b (e.g., simultaneously), both a and c (e.g., simultaneously), both b and c (e.g., simultaneously), all of a, b, and c, or variations thereof.

[0038] In this disclosure, the terms “comprise(s) / comprising,” “include(s) / including,” or “have / has / having” should be understood to specify the presence of the stated features, integers, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Furthermore, the terms “comprise(s) / comprising,” “include(s) / including,” “have / has / having,” or similar terms include or support the terms “consisting of” and “consisting essentially of,” indicating the presence of the stated features, integers, steps, operations, elements, and / or components, without or substantially without the presence of other features, integers, steps, operations, elements, components, and / or groups thereof.

[0039] In the context of this application and unless otherwise defined, the terms “use,” “using,” and “used” may be considered synonymous with the terms “utilize,” “utilizing,” and “utilized,” respectively.

[0040] As used herein, the terms “substantially,” “about,” or similar terms are used as approximate terms rather than terms of degree and are intended to describe inherent biases in measured or calculated values ​​that would be recognized by a person skilled in the art. “About,” as used herein, encompasses the stated value and refers to a specific value within an acceptable range of deviation determined by a person skilled in the art, taking into account the measurement in question and errors associated with the measurement of that particular quantity (e.g., limitations of the measurement system). For example, “about” may mean within one or more standard deviations or within ±30%, ±20%, ±10%, or ±5% of the stated value. Furthermore, it should be understood that even if the terms “about,” “approximately,” or “substantially” are not explicitly stated in a given element (e.g., a claim element), the scope of such elements is intended to include minor variations or variations understood by a person skilled in the art. For example, the numerical values ​​and ranges provided herein are intended to include tolerances and measurement uncertainties that would be recognized by a person skilled in the art, and elements (e.g., claim elements) should be interpreted accordingly to cover such equivalents.

[0041] Any numerical range described herein is intended to include all subranges containing the same numerical precision within the stated range. For example, the range “1.0 to 10.0” is intended to include all subranges between (and including) the minimum value of 1.0 and the maximum value of 10.0, such as a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, for example, 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits contained therein, and any minimum numerical limit described in this disclosure is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to modify the disclosure (including the claims) to expressly describe any subranges contained within the scope expressly described herein.

[0042] For clarity of illustration, descriptions and relationships may not be provided, and throughout the disclosure, substantially identical or similar configurations or arrangements of components may be designated by the same reference numerals. Furthermore, since the size and thickness of each configuration or arrangement shown in the figures are arbitrarily illustrated for better understanding and ease of description, embodiments of the present disclosure are not necessarily limited thereto.

[0043] In the accompanying drawings, the thickness of layers, films, panels, areas, etc., can be magnified for clarity. In the accompanying drawings, the thickness of a portion of a layer, area, etc., can be magnified for better understanding and easier description.

[0044] It will be understood that if (for example, when) a component (e.g., a layer, film, region, or substrate) is referred to as "on" or "above" another component, it may be directly on or directly above the other component, or there may be intervening components therein. Conversely, if (for example, when) a component is referred to as "directly on" or "directly above" another component, there are no intervening components therein.

[0045] In this paper, the Hansen solubility parameter (HSP) is a value used to predict the solubility of materials. The Hansen solubility parameter reflects the physicochemical solubility properties of organic materials, also known as their solubility. HSP is based on the concept that "two materials with similar intermolecular interactions may dissolve in each other."

[0046] The Hansen solubility parameters can be calculated according to the method presented by Charles Hansen in *Hansen Solubility Parameters: A User's Manual*, 2nd Edition (2007), Boca Raton, Florida: CRC Press. ISBN 978-0-8493-7248-3. According to this method, three parameters, δd, δp, and δh, referred to as the "Hansen parameters," are sufficient or suitable for predicting the solvent behavior of a given molecule. At MPa 1 / 2 At this point, the parameter δd can quantify the energy of intermolecular dispersion forces, such as van der Waals forces. At MPa 1 / 2 At this point, the parameter δp can represent the energy of the intermolecular dipole interaction. Furthermore, at MPa... 1 / 2 The parameter δh can quantify the energy from intermolecular hydrogen bonds, such as the ability to interact via hydrogen bonds.

[0047] These three parameters can be viewed as coordinates in three-dimensional space (Hanssen space). If (for example, when) the HSPs of two materials are placed in Hansen space, the closer the distance between the two points, the more likely they are to dissolve into each other.

[0048] Because HSP is a vector quantity, it may rarely have exactly the same value in pure (e.g., substantially pure) materials. Furthermore, databases of HSPs for commonly used materials have been established. Therefore, those skilled in the art can obtain the HSP value of the desired material by referring to these databases.

[0049] Even if (for example) a material does not have an HSP value registered in a database, the HSP value can be calculated from its chemical structure using computer software (such as COSMOquick).

[0050] For example, if (e.g., when) the molecule's smiles code is input as input data, the database value can be predicted if (e.g., when) the molecule's HSP exists in the COSMOquick database, and if (e.g., when) it does not exist in the database, the molecule's HSP value can be predicted using its own prediction equation.

[0051] The following describes in more detail a developer composition applied to a metal-containing photoresist according to one or more embodiments.

[0052] In a developer composition for a metal-containing photoresist according to one or more embodiments,

[0053] Coordinate a, which ranges from 9 to 12 mJ / cm 2 The first exposure energy is specified by the Hansen solubility parameters (δd, δp, and δh) of the first photoresist containing the metal photoresist.

[0054] Coordinate b, which is 5 to 10 mJ / cm² higher than the first exposure energy. 2 The second exposure energy is specified by the Hansen solubility parameters (δd, δp, and δh) of the second photoresist containing the metal photoresist; and

[0055] The coordinate x, specified by the Hansen solubility parameters (δd, δp, and δh) of the developer composition,

[0056] The solubility radius Ra, centered at coordinate a, can be calculated.

[0057] The solubility radius Rb can be calculated with coordinate b as the center value (e.g., another center value), and

[0058] The distance between coordinates x and a calculated by Equation 1 and Equation 2 respectively. ) and the distance between coordinates x and b ( It can have relational expressions. < Ra and > Rb.

[0059] Equation 1

[0060] = 4(δd x - δd a ) 2 + (δp x - δp a ) 2 + (δh x - δh a ) 2

[0061] Equation 2

[0062] = 4(δd x - δd b ) 2 + (δp x - δp b ) 2 + (δh x - δh b ) 2

[0063] Hansen solubility parameters (HSP), solubility radius Ra, and solubility radius Rb can be predicted using the Generate Hansen Parameters module in the COSMOquick version 22 program.

[0064] The Hansen solubility parameter (HSP) is an indicator of a material's dispersion, polarity, and hydrogen bonding, and is useful for determining the compatibility between materials. The solubility between materials is expressed numerically based on the material's dispersion force (δd), polar force (δp), and hydrogen bonding force (δh), and each material is located in three-dimensional space using δd, δp, and δh factors as axes.

[0065] It is understandable that the target photoresist undergoes structural and compositional changes upon dissolution due to energy irradiation, and these changes also cause variations in solubility parameters. By distinguishing the changing solubility based on the irradiation energy and calculating the Hansen parameter through simulation, the positional values ​​of the parameter that vary according to the material's structural state and composition can be compared.

[0066] Whether a photoresist has been dissolved can be determined by comparing the thickness after it has been coated with an energy-irradiated photoresist to a specific (e.g., set or predetermined) thickness and dissolved using a developer composition as described in one or more embodiments.

[0067] At the same time, by calculating the unique (e.g., different) solubility radii (Ra, Rb) of each material and the two components ( and The distance between the two components allows for the quantification of their solubility.

[0068] At this point, the distance between the two components in space ( and The smaller the value, the higher the compatibility between them, such as solubility.

[0069] Figure 2 This is a schematic diagram illustrating the solubility range of each photoresist based on exposure energy by performing simulations on the components according to this disclosure.

[0070] Reference Figure 2 The high solubility areas in the unexposed parts are indicated by ① and ④, while the high solubility areas in the exposed parts are indicated by ② and ④.

[0071] At this point, the region where the unexposed portion has high solubility but the exposed portion has low solubility, and the difference in solubility between the unexposed and exposed portions is significantly or substantially comparable, is the region indicated by ①. The developer composition implemented in this disclosure has parameters for the region indicated by ①. Regions ②, ③, and ④ can be defined as regions where sensitivity is reduced or where scum and bridging occur compared to region ①.

[0072] Meanwhile, region ③ refers to the region where both the unexposed and exposed parts have low solubility (e.g., simultaneously).

[0073] The developer composition for metal-containing photoresists according to one or more embodiments may include at least one selected from ethers, alcohols, glycol ethers, aromatic hydrocarbon compounds, ketones, and esters, but the embodiments of this disclosure are not limited thereto. For example, organic solvents may include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether, propylene glycol butyl ether acetate, ethanol, propanol, isopropanol, isobutanol, 2-butanol, 4-methyl-2-pentanol (or may be called methyl isobutyl methanol (MIBC)), hexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butenyl carbonate, toluene, dimethyl ether, etc. Benzene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, acetylacetone, acetic acid, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propylacetate, methyl methoxypropionate, ethyl ethoxypropionate, or mixtures thereof, but the embodiments disclosed herein are not limited thereto.

[0074] The developer composition for metal-containing photoresists according to one or more embodiments may further include at least one other additive selected from organic acids, surfactants, dispersants, hygroscopic agents and coupling agents.

[0075] Furthermore, according to one or more embodiments, the method of forming or providing a pattern may include a development method using a developer composition for a metal-containing photoresist as described in one or more embodiments. For example, the pattern produced may be a negative photoresist pattern.

[0076] A method for forming or providing a pattern according to one or more embodiments may include coating a metal-containing photoresist composition on a substrate, performing a heat treatment wherein a metal-containing photoresist film is formed or provided on the substrate by drying and heating, exposing the metal-containing photoresist film, and developing it using a developer composition for the metal-containing photoresist.

[0077] For example, forming or providing a pattern using a metal-containing photoresist composition may include coating a metal-containing photoresist composition on a substrate on which a thin film is formed or provided by spin coating, slot coating, inkjet printing and / or similar methods, and drying the coated metal-containing photoresist composition to form or provide a resist layer.

[0078] Metal-containing photoresist compositions may include organometallic compounds containing at least one selected from organic oxygen and organic carbonyl oxygen.

[0079] For example, organometallic compounds may include at least one metal selected from tin (Sn), tellurium (Te), and antimony (Sb).

[0080] For example, organometallic compounds may include Sn.

[0081] In one or more embodiments, the metal-containing photoresist composition may include an organotin compound represented by chemical formula 1.

[0082] [Chemical Formula 1]

[0083]

[0084] In chemical formula 1,

[0085] R 6 The substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and substituted or unsubstituted C7 to C30 aralkyl are optional.

[0086] R 7 To R 9 Each can independently be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C7 to C30 aralkyl, an alkoxy, or an aryloxy (-OR)b , where R b The substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof, and carboxyl (-O(CO)R) c , where R c It can be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylamide or dialkylamide (-NR). d R e , where R d and R e Each of the following groups is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), or an amide group (-NR). f (COR g ), where R f and R g Each of the following is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), and amidine (-NR) h C(NR i )R j , where R h R i and R j Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylthio or arylthio (-SR). k , where R k (Substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof) or thiocarboxyl (-S(CO)R) l , where R l(which may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof), and

[0087] R 7 To R 9 At least one of the selected components may be an alkoxy or an aryloxy (-OR) b , where R b The substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof, and carboxyl (-O(CO)R) c , where R c It can be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylamide or dialkylamide (-NR). d R e , where R d and R e Each of the following groups is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof), or an amide group (-NR). f (COR g ), where R f and R g Each of the following is independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof), and amidine (-NR) h C(NR i )R j , where R h R i and R j Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, alkylthio or arylthio (-SR). k , where R k(Substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof) or thiocarboxyl (-S(CO)R) l , where R l It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

[0088] For example, R 7 To R 9 At least one of the selected options may be selected from alkoxy or aryloxy (-OR) b , where R b The substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof) and carboxyl (-O(CO)R) groups. c , where R c It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

[0089] For example, R 6 It may be a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C2 to C8 aliphatic unsaturated organic group including one or more double bonds and / or triple bonds, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C4 to C20 heteroaryl group, a carbonyl group, an ethoxy group, a propoxy group, or a combination thereof.

[0090] R b It may be a substituted or unsubstituted C1 to C8 alkyl, a substituted or unsubstituted C3 to C8 cycloalkyl, a substituted or unsubstituted C2 to C8 alkenyl, a substituted or unsubstituted C2 to C8 alkynyl, a substituted or unsubstituted C6 to C20 aryl, or a combination thereof, and

[0091] R c It may be hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

[0092] In one or more embodiments, the metal-containing photoresist composition may include an organotin compound represented by chemical formula 2 or chemical formula 3.

[0093] Chemical formula 2

[0094] R 10 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0095] In chemical formula 2,

[0096] R 10 It can be a C1 to C31 hydrocarbon group, 0 < z ≤ 2, and 0 < (z+x) ≤ 4;

[0097] Chemical formula 3

[0098] R 11 a Sn b X c Y d

[0099] In chemical formula 3,

[0100] R 11 It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group including one or more double bonds and / or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof.

[0101] X can be sulfur (S), selenium (Se), or tellurium (Te).

[0102] Y can be -OR m or -OC(=O)R n ,

[0103] Where R m It is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0104] R n It is hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0105] a, b, c, and d can each be an integer from 1 to 20 independently.

[0106] Subsequently, a first heat treatment process can be performed to heat and form or provide a substrate containing a metal photoresist film. The first heat treatment process can be performed at a temperature of approximately 80 degrees Celsius to approximately 120 degrees Celsius. In this process, the solvent can be evaporated and the metal photoresist film can be more firmly or properly adhered to the substrate.

[0107] Then, the photoresist film is selectively exposed.

[0108] Examples of light that can be used in exposure processes include not only light with relatively low energy wavelengths, such as i-line (365 nm), KrF excimer laser (248 nm) and / or ArF excimer laser (193 nm), but also light with relatively high energy wavelengths, such as extreme ultraviolet (EUV, 13.5 nm), as well as other light sources, such as electron beams (e-beam) and / or the like.

[0109] For example, the light used for exposure according to one or more embodiments may be light with a relatively high energy wavelength in the range of about 5 nanometers to about 150 nanometers, such as extreme ultraviolet (EUV, wavelength 13.5 nanometers), and other light sources such as electron beams (e-beams) and / or the like.

[0110] In methods for forming or providing photoresist patterns, negative patterns may be formed or provided.

[0111] The exposed portions of a photoresist film can be formed or provided with polymers through cross-linking reactions (e.g., condensation between organometallic compounds), and thus can have different solubility than the unexposed portions of the photoresist film.

[0112] Then, a second heat treatment process can be performed on the substrate. The second heat treatment process can be performed at a temperature of about 90 degrees Celsius to about 200 degrees Celsius. By performing the second heat treatment process, the exposed portions of the photoresist film can become less soluble in the developer.

[0113] For example, a photoresist pattern corresponding to a negative-tone image can be created by dissolving and then removing the photoresist film corresponding to the unexposed portion using a photoresist developer as described in one or more embodiments.

[0114] As described in one or more embodiments, the photoresist pattern formed or provided can have a thickness of about 5 nanometers to about 100 nanometers by exposing it not only to light with relatively low energy wavelengths, such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and / or ArF excimer laser (wavelength 193 nm), but also to light with relatively high energy wavelengths, such as extreme ultraviolet (EUV; wavelength 13.5 nm), and other light sources, such as electron beams (e-beams). For example, the photoresist pattern can be formed or provided to have a thickness of about 5 nanometers to about 90 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 60 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 40 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers.

[0115] In one or more embodiments, the photoresist pattern may have a pitch half-pitch of less than or equal to about 50 nanometers, for example less than or equal to about 40 nanometers, for example less than or equal to about 30 nanometers, for example less than or equal to about 20 nanometers, for example less than or equal to about 15 nanometers, and a linewidth roughness of less than or equal to about 10 nanometers, less than or equal to about 5 nanometers, less than or equal to about 3 nanometers, or less than or equal to about 2 nanometers.

[0116] The method of forming or providing a pattern is described in more detail below with reference to the accompanying drawings.

[0117] Figures 1A-1C A cross-sectional view is provided to illustrate the process steps in order to describe the method of forming or providing a pattern.

[0118] Reference Figure 1A It can develop exposed photoresist films to form or provide photoresist patterns 130P.

[0119] In one or more embodiments, an exposed photoresist film can be developed to remove unexposed portions of the photoresist film, and a photoresist pattern 130P including exposed portions of the photoresist film can be formed or provided. The photoresist pattern 130P may include a plurality of openings OP.

[0120] In one or more embodiments, the development of the photoresist film can be performed using a negative-tone development (NTD) process. Throughout this document, a developer composition for metal-containing photoresist according to one or more embodiments can be used as a developer composition.

[0121] Reference Figure 1B 130P photoresist pattern can be used for processing Figure 1A The result is feature layer 110.

[0122] For example, feature layer 110 can be processed by one or more of the following suitable processes: etching feature layer 110 exposed through opening OP of photoresist pattern 130P, implanting impurity ions into feature layer 110, forming or providing an additional thin film on feature layer 110 through opening OP, partially deforming feature layer 110 through opening OP, and / or the like. Figure 1B A method is shown for processing a feature pattern 110P by etching a feature layer 110 exposed through an opening OP.

[0123] Reference Figure 1C , can Figure 2 The result is the removal of the photoresist pattern 130P remaining on the feature pattern 110P. To remove the photoresist pattern 130P, an ashing and stripping process can be used. The feature pattern 110P is located on the substrate 100.

[0124] Hereinafter, one or more embodiments of the present disclosure will be described in more detail by way of examples relating to the preparation of developer compositions for metal-containing photoresists as described in one or more embodiments. However, the embodiments of the present disclosure are not limited to the following examples.

[0125] Example

[0126] An organometallic compound (a 21-Sn molecule cluster ((t-Bu)3Sn3(O2CH)5(OH)2O)) was dissolved at a concentration of 3% in propylene glycol methyl ether acetate (PGMEA), and then filtered through a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare a semiconductor photoresist composition. This composition was spin-coated onto an 8-inch wafer at 1,500 rpm for 30 seconds, followed by heat treatment at 160°C for 60 seconds to fabricate a coated wafer. The coated wafer exhibited a temperature of 7 mJ / cm². 2 Up to 25 mJ / cm 2 The process involves progressively performing KrF exposure and post-exposure bake (PEB) within the exposure energy range.

[0127] Subsequently, a development process is performed on each exposure energy method (e.g., step) to fabricate a thin film on which a pattern is formed or provided, using a developer composition comprising the corresponding solvents as shown in Table 1, and the thickness of the dissolved film is measured, which is used to obtain a relative thickness expressed as a contrast curve (developed photoresist film thickness after exposure at the second exposure energy / developed photoresist film thickness after exposure at the first exposure energy), and after classifying film thicknesses less than or equal to 20% as soluble but film thicknesses greater than 20% as insoluble from the contrast curve to obtain solubility data for at least 5 solvents, this data is used to calculate HSP spheres. Hansen solubility parameter simulation, which uses the methodology proposed in the paper “Calculating Hansen solubility parameters of polymers with genetic algorithms” G. CañeteVebber et al., J. Appl. Polym. Sci., 2014, is performed by fitting data to maximize or increase the solubility fraction, obtaining the solubility factor and soluble radii Ra and Rb of the photoresist, and thus obtaining the solubility factor and soluble radii Ra and Rb of the photoresist, and thus obtaining the solubility parameters of the photoresist. < Ra and > The scope of the Rb relation.

[0128] Table 1

[0129]

[0130] Developer composition

[0131] S1: Acetylacetone (AcAc)

[0132] S2: Propylene glycol methyl ether acetate (PGMEA) / AcAc = 90 / 10 (wt% / wt%)

[0133] S3: Propylene glycol methyl ether acetate (PGMEA) / AcAc = 80 / 20 (wt% / wt%)

[0134] S4: Propylene glycol methyl ether acetate (PGMEA) / AcAc = 70 / 30 (wt% / wt%)

[0135] S5: γ-Butyrolactone (GBL)

[0136] S6: GBL / AcAc = 80 / 20 (weight% / weight%)

[0137] S7: PGMEA

[0138] S8: Acetic acid (AA)

[0139] S9: n-Butyl acetate

[0140] S10: Methyl isobutyl methanol (MIBC)

[0141] S11: PGMEA / AA = 98 / 2 (weight% / weight%)

[0142] S12: PGMEA / AA = 60 / 40 (weight% / weight%)

[0143] S13: 2-Heptanone

[0144] S14: 2-Butanol

[0145] S15: Anisole (or methoxybenzene)

[0146] Assessment: Sensitivity / Scum and Bridging Assessment

[0147] The prepared organic metal semiconductor photoresist composition was spin-coated on an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 160°C for 60 seconds to produce a coated wafer.

[0148] Subsequently, a linear array of 50 circular pads, each 500 micrometers in diameter, was projected onto a wafer coated with a photoresist developer composition using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET). The exposure time of the pads was controlled so that an increasing dose of EUV was applied to each pad.

[0149] Subsequently, the photoresist and substrate were exposed on a hot plate at 160°C for 120 seconds, and then baked. The baked film was developed by applying the respective developer compositions of Examples 1 to 6 and Comparative Examples 1 to 9 at a rotation speed of 1,500 rpm for 30 seconds, and then cured at 240°C for 60 seconds.

[0150] As a result, an L / S (=1:1) pattern with a linewidth of 50 nanometers is formed or provided.

[0151] To obtain the optimal exposure dose Eop (μC / cm) for forming or providing an LS pattern with the target size. 2 ).

[0152] When using the optimal exposure dose Eop (μC / cm) 2 When reducing the irradiation dose to reduce space size, the minimum dose required to form or provide a defect-free pattern (such as scum, bridging and / or the like) is defined as E0, which is shown in Table 2.

[0153] The photoresist linewidth was measured using CD-SEM to measure changes in exposure dose (energy). The appropriate sensitivity E of the exposure dose was then checked based on the different photoresist linewidths at various exposure doses. gel In addition, CD-SEM images were used to examine the extent of scum and bridging formation, and the results are shown in Table 2.

[0154] Table 2

[0155]

[0156] Referring to Table 2, in Examples 1 to 6, E0 and E gel The sensitivity was reduced and improved or enhanced, while no scum and bridging were observed.

[0157] In the foregoing, certain embodiments of this disclosure have been described and illustrated. However, it will be apparent to those skilled in the art that this disclosure is not limited to the embodiments as described, and that appropriate modifications and transformations may be made without departing from the spirit and scope of this disclosure. Therefore, modified or transformed embodiments may not be understood solely from the technical conception and aspects of the embodiments of this disclosure, and the modified embodiments are within the scope of the appended claims and their equivalents.

Claims

1. A developer composition for use with metal-containing photoresist, The developer composition is applied to the metal-containing photoresist. Coordinate a is changed from the first exposure energy of 9 to 12 mJ / cm 2 The Hansen solubility parameters δd, δp, and δh of the first photoresist exposed to the metal-containing photoresist are specified. Coordinate b is specified by the Hansen solubility parameters δd, δp, and δh of the second photoresist containing the metal, exposed at a second exposure energy 5 to 10 mJ / cm² higher than the first exposure energy. 2 ; as well as For coordinate x, specified by the Hansen solubility parameters δd, δp, and δh of the developer composition. The solubility radius R with the coordinate a as its center value a Calculated The solubility radius R with the coordinate b as another center value b Calculated, and The distance between the coordinate x and the coordinate a calculated by Equations 1 and 2 respectively. and the distance between the coordinate x and the coordinate b Having a relation < Ra and > Rb; [Equation 1] = 4(δd x - δd a ) 2 + (δp x - δp a ) 2 + (δh x - δh a ) 2 [Equation 2] = 4(δd x - δd b ) 2 + (δp x - δp b ) 2 + (δh x - δh b ) 2 。 2. The developer composition for metal-containing photoresist according to claim 1, wherein: The developer composition includes ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosol acetate, ethyl cellosol acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether, propylene glycol butyl ether acetate, ethanol, propanol, isopropanol, isobutanol, 2-butanol, 4-methyl-2-pentanol, hexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, toluene, xylene, methyl ethyl ketone, and cyclohexane. Pentanone, cyclohexanone, 2-heptanone, acetylacetone, acetic acid, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, or mixtures thereof.

3. The developer composition for metal-containing photoresist according to claim 1, wherein: The developer composition includes acetylacetone, propylene glycol methyl ether acetate, γ-butyrolactone, acetic acid, n-butyl acetate, methyl isobutyl methanol, 2-heptanone, 2-butanol, methoxybenzene, or combinations thereof.

4. The developer composition for metal-containing photoresist according to claim 2, wherein: The developer composition further includes at least one additive selected from organic acids, surfactants, dispersants, hygroscopic agents and coupling agents.

5. A method for forming a pattern, comprising: A metal photoresist composition is coated onto a substrate; Heat treatment is performed by drying and heating, wherein a metal photoresist film is contained on the substrate; Expose the metal-containing photoresist film; and Development is performed using the developer composition for metal-containing photoresist as described in any one of claims 1 to 4.

6. The method according to claim 5, wherein: The metal-containing photoresist composition includes an organometallic compound, which includes at least one selected from organooxy and organocarbonyloxy groups.

7. The method according to claim 6, wherein: The organometallic compound includes at least one metal selected from Sn, Te, and Sb.

8. The method according to claim 6, wherein: The organometallic compound includes Sn.

9. The method according to claim 5, wherein: The metal-containing photoresist composition includes an organotin compound represented by chemical formula 1: [Chemical Formula 1] In chemical formula 1, R 6 Selected from substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, and substituted or unsubstituted C7 to C30 aralkyl. R 7 To R 9 Each of the following is independently a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C7 to C30 aralkyl, or -OR b -O(CO)R c -NR d R e -NR f (COR g -NR h C(NR i )R j -SR k or -S(CO)R l , Where R b It can be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R c It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R d and R e Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R f and R g Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R h R i and R j Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R k It can be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R l It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof, and R 7 To R 9 At least one of the selected options is -OR b -O(CO)R c -NR d R e -NR f (COR g -NR h C(NR i )R j -SR k or -S(CO)R l , Where R b It can be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R c It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R d and R e Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R f and R g Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R h R i and R j Each of the following is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R k It can be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R l It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

10. The method according to claim 9, wherein: R 7 To R 9 At least one of them is selected from -OR b and -O(CO)R c , Where R b It can be a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, or a combination thereof. Where R c It is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof.

11. The method according to claim 7, wherein: R 6 The substituted or unsubstituted C1 to C8 alkyl groups, substituted or unsubstituted C3 to C8 cycloalkyl groups, substituted or unsubstituted C2 to C8 aliphatic unsaturated organic groups including one or more double or triple bonds, substituted or unsubstituted C6 to C20 aryl groups, substituted or unsubstituted C4 to C20 heteroaryl groups, carbonyl groups, ethoxy groups, propoxy groups, or combinations thereof. R b The substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or combinations thereof, and R c It is hydrogen, substituted or unsubstituted C1 to C8 alkyl, substituted or unsubstituted C3 to C8 cycloalkyl, substituted or unsubstituted C2 to C8 alkenyl, substituted or unsubstituted C2 to C8 alkynyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

12. The method according to claim 5, wherein: The metal-containing photoresist composition includes an organotin compound represented by chemical formula 2 or chemical formula 3: [Chemical Formula 2] R 10 z SnO (2-(z / 2)-(x / 2)) (OH) x , In chemical formula 2, R 10 For C1 to C31 hydrocarbon groups, 0 < z ≤ 2, and 0 < (z+x) ≤ 4; [Chemical Formula 3] R 11 a Sn b X c Y d , In chemical formula 3, R 11 The group may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group including one or more double or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof. X represents sulfur, selenium, or tellurium. Y is -OR m or -OC(=O)R n , Where R m The substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or combinations thereof, and R n The alkyl group is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof. a, b, c, and d are each independent integers from 1 to 20.

13. The method according to claim 5, wherein: The pattern is a negative pattern.

14. The method according to claim 5, wherein: The pattern has a thickness of 5 nanometers to 100 nanometers.

15. The method according to claim 5, wherein: The pattern has a half-pitch of less than or equal to 50 nanometers.

16. The method according to claim 5, wherein: The pattern has a linewidth roughness of less than or equal to 10 nanometers.

17. The method according to claim 5, wherein: The heat treatment includes performing a first heat treatment at a temperature of 80°C to 120°C.

18. The method according to claim 5, wherein: The heat treatment includes performing a second heat treatment at a temperature of 90°C to 200°C.

19. The method according to claim 5, wherein: The exposure of the metal-containing photoresist film is to expose the metal-containing photoresist film to light with a wavelength in the range of 5 nanometers to 150 nanometers.

20. The method according to claim 5, wherein: The exposure of the metal-containing photoresist film is achieved by exposing the metal-containing photoresist film to an i-line, a KrF excimer laser, an ArF excimer laser, extreme ultraviolet light, an electron beam, or a combination thereof.

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