Developer composition for metal-containing photoresist and method for forming pattern including developing stage using the same

Abstract

Disclosed are a developer composition for a metal-containing photoresist and a method of forming a pattern using the developer composition. The developer composition may include a metal compound, an organic solvent, and an additive, and may be applied to a metal-containing photoresist having an exposed portion and a non-exposed portion. In the non-exposed portion, the number of hydrogen bonds between the metal compound and the organic solvent in the metal-containing photoresist may be greater than 0 and less than or equal to about 10 relative to the number of hydrogen bonds between the metal compound and the additive, and the number of hydrogen bonds between the additive and the organic solvent in the metal-containing photoresist may be greater than 0 and less than or equal to about 5 relative to the number of hydrogen bonds between the metal compound and the additive.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0121008, filed on September 5, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] One or more embodiments of this disclosure relate to a developer composition for a metal photoresist and a method of forming a pattern including a development step (e.g., action or task) using the developer composition. Background Technology

[0004] The semiconductor industry has experienced a continuous reduction in critical dimensions, which has made it necessary to develop high-performance photoresist materials and patterning methods that can support increasingly smaller features.

[0005] Chemically amplified (CA) photoresists are designed for high sensitivity. However, the typical elemental composition of CA photoresists—often including oxygen (O), fluorine (F), sulfur (S), and carbon (C)—results in low absorbance at a wavelength of approximately 13.5 nm, thus reducing sensitivity under extreme ultraviolet (EUV) exposure. Furthermore, particularly due to the nature of acid-catalyzed processes where line edge roughness (LER) increases with decreasing photospeed, CA photoresists tend to exhibit increased LER at smaller feature sizes. These limitations highlight the need for novel types of high-performance photoresists.

[0006] Therefore, there is a need or expectation for photoresist materials that simultaneously enhance sensitivity, critical dimension (CD) uniformity, and LER characteristics in photolithography processes while providing improved etch resistance and resolution. Summary of the Invention

[0007] One or more aspects of embodiments of this disclosure relate to a developer composition for a metal-containing photoresist.

[0008] One or more aspects of embodiments of this disclosure relate to a method of forming a pattern, the method comprising a development step (e.g., action or task) using a developer composition for a metal photoresist.

[0009] Additional aspects of the embodiments will be described in the following description and in part will become apparent to those skilled in the art from the following description, or can be learned by practice of the presented embodiments of the disclosure.

[0010] According to one or more embodiments, a developer composition for a metal-containing photoresist is provided. The developer composition is applied to a metal-containing photoresist having exposed portions and non-exposed portions, and includes:

[0011] a metal compound; an organic solvent; and an additive.

[0012] In the non-exposed portions of the photoresist, the number of hydrogen bonds between the metal compound and the organic solvent is greater than 0 and less than or equal to about 10 relative to the number of hydrogen bonds between the metal compound and the additive in the metal-containing photoresist.

[0013] Additionally, the number of hydrogen bonds between the additive and the organic solvent is greater than 0 and less than or equal to about 5 relative to the number of hydrogen bonds between the metal compound and the additive in the metal-containing photoresist.

[0014] The number of hydrogen bonds is determined by averaging the counts for each frame from a molecular dynamics simulation using the following parameters:

[0015] Molecular dynamics program: Materials Science Suites, Desmond module;

[0016] Force field applied for calculations: Optimized Potentials for Liquid Simulation (OPLS) 3e (OPLS3e); and

[0017] Simulation conditions: isobaric-isothermal (NPT) simulation, 50 ns, 300 K, 1 atm.

[0018] According to one or more embodiments, a method of forming a pattern includes:

[0019] applying a metal-containing photoresist composition on a substrate; performing a thermal treatment to form a photoresist film on the substrate (by drying and heating), exposing the metal-containing photoresist film; and developing the exposed film with a developer composition for a metal-containing photoresist.

[0020] The developer compositions for metal-containing photoresists according to one or more embodiments have improved or optimized elements through simulation to maximize or increase the separation of the metal compounds contained in the photoresist. Improved or enhanced solubility in the non-exposed portions can be achieved by applying a developer composition that meets these criteria. For example, the developer composition can be enhanced by modulating intermolecular interactions at the molecular level to promote selective solubility in the non-exposed portions of the metal-containing photoresist. This enhancement can be guided by molecular dynamics simulations that quantify the hydrogen bonding behavior between the metal compound, the organic solvent, and the additive. Favorable interaction profiles can be achieved by ensuring that the number of hydrogen bonds between the metal compound and the organic solvent falls within a defined range (greater than 0 and less than or equal to about 10) relative to the number of hydrogen bonds between the metal compound and the additive, and ensuring that the number of hydrogen bonds between the additive and the organic solvent is greater than 0 and less than or equal to about 5 relative to the number of hydrogen bonds between the metal compound and the additive.

[0021] These hydrogen bond parameters are not arbitrary; they are derived from simulations performed using the Desmond module of the Materials Science Suite under NPT conditions (50 ns, 300 K, 1 atm) with an OPLS3e force field applied. The simulation results provide an average hydrogen bond count per frame, which is used as a predictive metric for the solubility behavior of the photoresist in the unexposed regions.

[0022] By applying a developer composition that meets these criteria, the method enhances the separation of the metal compound from the unexposed photoresist matrix. This improves or enhances the solubility of the unexposed portions, thereby increasing development contrast, reducing line edge roughness (LER), and improving or enhancing critical dimension (CD) control—a key performance metric in advanced lithography processes. Attached Figure Description

[0023] The accompanying drawings, together with the description, illustrate embodiments of the subject matter of this disclosure and, together with the description, serve to explain the principles of the embodiments of the subject matter of this disclosure.

[0024] Figures 1A to 1C This is a cross-sectional view showing the process sequence to describe the method of forming the pattern.

[0025] Figure 2 This is a schematic diagram illustrating the distribution of the entire composition of metal compounds, organic solvents and additives in a metal-containing photoresist in a non-exposed portion for performing molecular dynamics calculations, according to one or more embodiments of the present disclosure.

[0026] Figure 3 It shows that it has been passed according to the law. Figure 2A schematic diagram of the distribution of the composition in equilibrium achieved through molecular dynamics simulation.

[0027] Explanation of icon numbers

[0028] 100: Substrate

[0029] 110: Feature Layer

[0030] 110P: Feature Pattern

[0031] 130P: Photoresist pattern

[0032] OP: Opening

[0033] (A): Metal compounds

[0034] (B): Organic solvent

[0035] (C): Additives Detailed Implementation

[0036] The subject matter of this disclosure will be described in more detail below with reference to the accompanying drawings. It should be understood that, in order to illustrate the features of this disclosure more clearly, certain functions, structures, or processes well known to those skilled in the art may be omitted or simplified in the following description.

[0037] When describing embodiments of this disclosure (e.g., in describing embodiments of this disclosure), the word "may" refers to "one or more embodiments of this disclosure".

[0038] Unless the context clearly indicates otherwise, the singular forms “a / an” and “the” as used herein are intended to also include the plural forms. Unless the context clearly indicates otherwise, singular expressions also include plural expressions.

[0039] The terms “and / or” or “or” as used in this document include any and all combinations of one or more of the relevant listed items.

[0040] Throughout this disclosure, expressions such as “at least one of…”, “one of…”, and “selected from”, when placed before a list of elements (e.g., when placed before a list of elements), modify the entire list, not 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 that only a is included, only b is included, only c is included, including (e.g., both a and b are included), including (e.g., both a and c are included), including (e.g., both b and c are included), including all of a, b, and c, or variations thereof.

[0041] In this disclosure, it should be understood that the terms "comprise(s) / comprising," "include(s) / including," or "have / has / having" specify the presence of the stated feature, integer, step, operation, element, and / or component, 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," "include," "have," or similar terms include or support the terms "consisting of" and "consisting essentially of," thereby indicating the presence of the stated feature, integer, step, operation, element, and / or component, while other features, integers, steps, operations, elements, components, and / or groups thereof are absent or substantially absent.

[0042] 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.

[0043] The terms “substantially,” “about,” or similar terms used herein are used as approximations rather than as terms of degree, and are intended to take into account the inherent biases of the measured or calculated values ​​that would be recognized by a person skilled in the art. “About” as used herein includes the stated value and refers to a value within an acceptable range of deviation from which a particular value would be determined by a person skilled in the art, taking into account the measurement in question and the errors associated with the measurement of the 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 when 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 non-substantialgesic variations or variations within the understanding of 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 one of ordinary skill in the art, and the elements (e.g., claim elements) should be interpreted accordingly to cover such equivalent forms.

[0044] Any numerical range described herein is intended to include all subranges of the same numerical precision falling within the stated range. For example, the range “1.0 to 10.0” is intended to include all subranges between the minimum value 1.0 and the maximum value 10.0 (and inclusive of the minimum value 1.0 and the maximum value 10.0), such as having 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 falling within it, and any minimum numerical limit described in this disclosure is intended to include all higher numerical limits falling within it. Therefore, the applicant reserves the right to amend this disclosure (including the claims) to expressly describe any subranges falling within the scope expressly described herein.

[0045] For clarity of illustration, no descriptions or relationships are provided, and throughout the disclosure, substantially identical or similar configurations or arrangements of elements may be indicated 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 illustration, embodiments of the present disclosure are not necessarily limited thereto.

[0046] In the diagrams, the thickness of each layer, membrane, panel, area, etc., may be exaggerated for clarity. In the diagrams, for better understanding and ease of explanation, the thickness of each layer, area, and / or part of a similar structure may be exaggerated.

[0047] It should be understood that when an element (e.g., a layer, film, region, or substrate) is referred to as being "on" or "above" another element (e.g., when an element (e.g., a layer, film, region, or substrate) is referred to as being "on" or "above" another element), the element may be directly on or directly above the other element, or there may be intermediate elements between the elements. In contrast, when an element is referred to as being "directly on" or "directly above" another element (e.g., when an element is referred to as being "directly on" or "directly above" another element), there are no intermediate elements between the elements.

[0048] Below, developer compositions for metal-containing photoresists according to one or more embodiments are described.

[0049] The developer composition for metal-containing photoresist according to one or more embodiments may be a developer composition applied to a metal-containing photoresist having exposed and unexposed portions, and

[0050] It contains metal compounds, organic solvents, and additives.

[0051] In the non-exposed portion,

[0052] In metal-containing photoresists, the number of hydrogen bonds between the metal compound and the organic solvent can be greater than 0 and less than or equal to about 10 relative to the number of hydrogen bonds between the metal compound and the additive.

[0053] In metal-containing photoresists, the number of hydrogen bonds between the additive and the organic solvent can be greater than 0 and less than or equal to about 5 relative to the number of hydrogen bonds between the metal compound and the additive.

[0054] The number of hydrogen bonds can be calculated by counting them in each frame after a molecular dynamics simulation and taking the average of the results for each frame:

[0055] Molecular Dynamics Program: Materials Science Suite, Desmond Module

[0056] Force fields applied to the computation: OPLS3e (OPLS3e refers to a version of the Optimized Liquid Simulation Potential (OPLS) force field. This force field can be used in molecular dynamics (MD) simulations to model molecular behavior by calculating the potential energy of the system based on atomic interactions), and

[0057] Simulation conditions: NPT simulation, 50 ns, 300 K, 1 atmosphere (NPT simulation refers to a type of constant molecular dynamics (MD) simulation: N: number of particles (atoms or molecules); P: pressure; and T: temperature. This is also known as an isothermal-isobaric ensemble).

[0058] This hydrogen bonding analysis provides a molecular-level understanding of how the developer composition interacts with photoresist components, for example, in non-exposed areas. By quantifying the relative strength and frequency of hydrogen bonds between metal compounds, organic solvents, and additives, formulations can be fine-tuned to achieve selective solubility. A higher number of hydrogen bonds between metal compounds and organic solvents, compared to the number between metal compounds and additives, promotes dissolution in non-exposed areas without adversely affecting exposed areas. This selective interaction is crucial for achieving high-resolution patterning in advanced photolithography processes, minimizing or reducing line edge roughness (LER), and ensuring uniform critical dimensions (CD).

[0059] For example, in a metal-containing photoresist, the number of hydrogen bonds between the metal compound and the organic solvent can be greater than 0 and less than or equal to about 8, for example greater than 0 and less than or equal to about 6, and for example greater than 0 and less than or equal to about 5.

[0060] For example, in a metal-containing photoresist, the number of hydrogen bonds between the metal compound and the organic solvent can be greater than 0 and less than or equal to about 4 relative to the number of hydrogen bonds between the metal compound and the additive, for example, greater than or equal to about 0.2 and less than or equal to about 4.

[0061] For example, in metal-containing photoresists, the number of hydrogen bonds between the additive and the organic solvent can be greater than 0 and less than or equal to about 4 relative to the number of hydrogen bonds between the metal compound and the additive.

[0062] The number of molecules in a metallic compound whose maximum intermolecular distance is less than or equal to about 3.5 Å can be greater than 0 and less than or equal to 10.

[0063] For example, the number of molecules in a metal compound whose maximum intermolecular distance is less than or equal to about 3.5 Å can be from about 1 to about 10 or less than 10, for example from about 2 to about 10 or less than 10, for example from about 3 to about 10 or less than 10, and for example from about 4 to about 10 or less than 10.

[0064] For example, the number of molecules in a metal compound with a maximum intermolecular distance of about 3.5 Å can be from about 5 to about 10.

[0065] The number of molecules can be calculated by counting each frame after a molecular dynamics simulation and taking the average of each frame.

[0066] For example, the metal compound may include at least one selected from tin (Sn), tellurium (Te), and antimony (Sb).

[0067] For example, metal compounds may contain Sn.

[0068] Examples of organic solvents included in developer compositions for metal-containing photoresists according to one or more embodiments may include at least one selected from ethers, alcohols, ethylene glycol ethers, aromatic hydrocarbons, ketones, and esters, but the embodiments disclosed herein are not limited thereto. For example, the organic solvent may include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celecoxib acetate, ethyl celecoxib 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, 4-methyl-2-pentanol (or methylisobutyl alcohol). Carbinol (MIBC), hexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butenyl carbonate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, ethoxyethyl acetate, hydroxyethyl acetate, 2-hydroxy-3-methylmethylbutyrate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxyethylpropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propane acetate, methyl methoxypropionate, ethyl ethoxypropionate, or combinations thereof, but the embodiments disclosed herein are not limited thereto.

[0069] Examples of additives included in a developer composition for a metal-containing photoresist according to one or more embodiments may include organic acids, phosphoric acid, phosphorous acid, diol compounds and / or diketone compounds, but the embodiments disclosed herein are not limited thereto.

[0070] The developer composition for metal-containing photoresist according to one or more embodiments may further include at least one other additive selected from surfactants, dispersants, hygroscopic agents and coupling agents.

[0071] In one or more embodiments, a method of forming a pattern may include a development step (e.g., action or task) 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 (negative-type) photoresist pattern.

[0072] A method for forming a pattern according to one or more embodiments may include: coating a metal-containing photoresist composition onto a substrate; performing a heat treatment in which a metal-containing photoresist film is formed 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. For example, the method may begin by applying a uniform layer formed from the metal-containing photoresist composition onto the substrate using techniques such as spin coating, slot coating, and / or inkjet printing. This may be followed by a soft baking or pre-baking step (e.g., an action or task) during which the coated substrate is heated to remove residual solvent and promote adhesion of the photoresist film to the substrate surface. After stabilizing the film (forming the film), the film may be exposed to a radiation source such as extreme ultraviolet (EUV), electron beam, or deep ultraviolet (DUV) light using a photomask or direct-write system to define the desired pattern. The exposed areas may undergo chemical transformations that alter their solubility, such as crosslinking. The substrate can then be subjected to a development step (e.g., action or task) using a developer composition as described in one or more embodiments, which selectively dissolves the non-exposed areas of the photoresist, thereby revealing patterned features with high fidelity.

[0073] For example, patterning using a metal-containing photoresist composition may include: coating the metal-containing photoresist composition onto a substrate, forming a thin film on the substrate by spin coating, slot coating, inkjet printing, and / or similar processes; and drying the coated metal-containing photoresist composition to form a resist layer. The metal-containing photoresist composition may contain a tin-based compound, and for example, the tin-based compound may include at least one selected from alkyltinoxy, alkyltin carboxyl, and alkyltin hydroxyl groups.

[0074] Subsequently, a first heat treatment process can be performed to heat the substrate on which the metal-containing photoresist film is formed. This first heat treatment process can be performed at a temperature of approximately 80°C to approximately 120°C. In this process, the solvent can be evaporated, and the metal-containing photoresist film can be more firmly or suitably bonded to the substrate. For example, this first heat treatment may also be referred to as soft baking or pre-baking and can play various roles in the patterning process. During subsequent processing, the first heat treatment can promote the controlled evaporation of residual solvent from the coated photoresist layer to achieve a uniform (e.g., substantially uniform) film thickness and prevent / reduce defects such as blistering and / or delamination. Furthermore, this thermal step (e.g., action or task) can promote partial densification of the metal-containing photoresist, thereby enhancing its mechanical stability and adhesion to the underlying substrate. The selected temperature range of approximately 80°C to approximately 120°C ensures sufficient or suitable solvent removal without triggering premature chemical reactions or degradation of the photoresist components. This step (e.g., action or task) can be used to ensure consistent exposure and development performance in subsequent stages of the photolithography process.

[0075] Then, the photoresist film can be selectively exposed.

[0076] Examples of light that can be used in exposure processes include not only light with relatively low energy wavelengths (e.g., i-line (wavelength 365 nm), KrF excited molecular laser (wavelength 248 nm) and / or ArF excited molecular laser (wavelength 193 nm)), but also light with relatively high energy wavelengths (e.g., extreme ultraviolet (EUV; wavelength 13.5 nm) and / or similar light) and other sources such as electron beams (e-beam) and / or the like.

[0077] For example, the light used for exposure according to one or more embodiments may be light with a wavelength range of about 5 nm to about 150 nm (e.g., extreme ultraviolet (EUV; wavelength of 13.5 nm) and / or similar light) and other sources (e.g., electron beam (e-beam)).

[0078] In the step (e.g., action or task) of forming a photoresist pattern, a negative (negative class) pattern can be formed.

[0079] The exposed portion of the photoresist film can form a polymer through cross-linking reactions (e.g., condensation) between various organometallic compounds, and thus can have a different solubility than the non-exposed portion of the photoresist film.

[0080] A second thermal processing step can then be performed on the substrate. This second thermal processing step can be performed at a temperature of approximately 90°C to approximately 200°C. For example, the second thermal processing step can also be referred to as post-exposure bake (PEB) and can be a step (e.g., action or task) following exposure of a metal-containing photoresist film. Depending on the specific formulation of the photoresist and the desired patterning result, this thermal process can be performed at a temperature ranging from approximately 90°C to approximately 200°C. The primary function of PEB can be to promote chemical reactions, such as crosslinking and / or condensation, within the exposed regions of the photoresist. These reactions can enhance structural integrity and reduce the solubility of the exposed regions, thereby enabling the formation of negative patterns during development. The increased temperature can accelerate the migration of active materials and promote the formation of robust polymer networks, for example, in metal-organic systems such as tin-based photoresists. Proper control of PEB conditions can be used to achieve high-resolution features, minimize / reduce line edge roughness (LER), and ensure consistent critical dimension (CD) control across the entire substrate.

[0081] By implementing a second heat treatment process, the exposed portion of the photoresist film can become less soluble in the developer.

[0082] For example, a photoresist pattern corresponding to a negative (negative class / negative type) image can be completed by dissolving and then removing the photoresist film corresponding to the unexposed portion using a photoresist developer as described in one or more embodiments.

[0083] As described in one or more embodiments, photoresist patterns formed by exposure not only to light with relatively low-energy wavelengths (e.g., i-line (wavelength 365 nm), KrF excited molecular laser (wavelength 248 nm), and / or ArF excited molecular laser (wavelength 193 nm)) but also to light with relatively high-energy wavelengths (e.g., extreme ultraviolet (EUV; wavelength 13.5 nm) and / or similar light) and other sources with high energy (e.g., electron beams (e-beams)) can have a thickness of about 5 nm to about 100 nm. For example, photoresist patterns can be formed to have thicknesses of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0084] In one or more embodiments, the photoresist pattern may have a half-pitch of less than or equal to about 50 nm, for example less than or equal to about 40 nm, for example less than or equal to about 30 nm, for example less than or equal to about 20 nm, for example less than or equal to about 15 nm, and the photoresist pattern may have a line width roughness of less than or equal to about 10 nm, less than or equal to about 5 nm, less than or equal to about 3 nm, or less than or equal to about 2 nm.

[0085] The method described herein leverages the customized hydrogen bonding interactions of the developer composition to achieve high-resolution patterning in metal-containing photoresists. By selectively dissolving unexposed areas while maintaining the integrity of the exposed crosslinked regions, the developer composition enables precise pattern transfer with minimal or reduced line edge roughness (LER) and excellent or suitable critical size (CD) control. This can be advantageous or beneficial for next-generation lithography technologies such as EUV and electron beam lithography, which require or expect features below 20 nm and tight process windows. The ability to form patterns with half-pitch below about 30 nm and LER values ​​below about 3 nm demonstrates the effectiveness of the developer composition in supporting advanced semiconductor manufacturing nodes.

[0086] In the following text, a method for forming a pattern is described in more detail with reference to the accompanying drawings.

[0087] Figures 1A to 1C This is a cross-sectional view showing the process sequence to describe the method of forming the pattern.

[0088] Reference Figure 1A It can develop the exposed photoresist film to form a photoresist pattern 130P.

[0089] In one or more embodiments, the exposed photoresist film may be developed to remove the unexposed portions of the photoresist film, and a photoresist pattern 130P including the exposed portions of the photoresist film may be formed. The photoresist pattern 130P may include a plurality of openings OP.

[0090] In one or more embodiments, the development of the photoresist film can be performed using a negative-tone development (NTD) process. In this document, the developer composition for metal-containing photoresist according to one or more embodiments can be used as a developer composition.

[0091] Reference Figure 1B 130P photoresist patterns can be used to... Figure 1A The feature layer 110 in the results shown is processed.

[0092] For example, the feature layer 110 may be processed by one or more of the following suitable processes: etching the feature layer 110 exposed by the opening OP of the photoresist pattern 130P, implanting impurity ions into the feature layer 110, forming an additional film on the feature layer 110 through the opening OP, deforming a portion of the feature layer 110 through the opening OP, and / or performing similar processes. Figure 1B An exemplary process is shown to process the feature pattern 110P by etching the feature layer 110 exposed via the opening OP.

[0093] Reference Figure 1C , can Figure 2 The results shown remove the photoresist pattern 130P retained on the feature pattern 110P. To remove the photoresist pattern 130P, an ashing process and / or a stripping process can be used. The feature pattern 110P is located on the substrate 100.

[0094] In the following, 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 described in one or more embodiments. However, the embodiments of the present disclosure are not limited to the following examples.

[0095] The molecular dynamics simulation results are shown in Table 1.

[0096] For molecular dynamics calculations, the Materials Science Suite program and the Desmond module were used to generate an initial composition containing organic solvents and additives. The number of additives and organic solvents was adjusted according to the additive conditions to ensure (e.g., such that) the total number of molecules of the metal compound, additives, and organic solvents was 2000. In this paper, the metal compound was designed to have a simulated structure for molecular dynamics simulations consisting of a cluster of 21 Sn molecules (e.g., (t-Bu)3Sn3(O2CH)5(OH)2O) (which is a trimer).

[0097] Figure 2 It represents an improved or optimized state of the initial composition.

[0098] Figure 2 This is a schematic diagram illustrating the distribution of the entire composition of metal compounds, organic solvents and additives in a metal-containing photoresist in a non-exposed portion for performing molecular dynamics calculations, according to one or more embodiments of the present disclosure.

[0099] Reference Figure 2 In the initial composition of the non-exposed portion, the metal compound (A) was not uniformly (e.g., substantially uniformly) distributed in the organic solvent (B) and additive (C), which confirms that no dissolution occurred by the developer.

[0100] Subsequently, equilibrium state calculations were performed for 50 ns using molecular dynamics simulations at 1 atmosphere and 300 K via NPT ensemble methods (e.g., thermostat method: Nose-Hoover chain, Barostat method: Martyna-Tobias-Klein). The compositional distribution at equilibrium is shown in this paper. Figure 3 middle.

[0101] Reference Figure 3 The composition that reaches equilibrium in the unexposed portion shows that the metal compound (A) is uniformly (e.g., substantially uniformly) distributed in the organic solvent (B) and additive (C), which confirms that dissolution has occurred sufficiently or appropriately by the developer.

[0102] In one or more embodiments, the number of hydrogen bonds was obtained by counting the number of hydrogen bonds between the metal compound and the organic solvent and additives in each frame of the entire unit and then calculating the average of the frame values.

[0103] Furthermore, the number of metal compounds was obtained by counting the number of molecules forming metal compounds within a distance of 3.5 Å in each frame after performing molecular dynamics simulations using the clustering analysis module of the Materials Science Suite program, and then calculating the average of the values ​​for each frame.

[0104] Table 1

[0105]

[0106] additive

[0107] C1: Propionic acid

[0108] C2: Succinic acid

[0109] C3: Fumaric acid

[0110] C4: Acetylacetone

[0111] C5: Trifluoroacetylacetone

[0112] C6: Methylphosphonic acid

[0113] C7: Maltol

[0114] C8: Phosphorous acid

[0115] C9: Cycloheptatrienolone

[0116] C10: Catechol

[0117] organic solvents

[0118] S1: n-Butyl acetate

[0119] S2: Propylene glycol methyl ether acetate (PGMEA)

[0120] S3: Methyl isobutyl methanol (MIBC)

[0121] Assessment: Defect Assessment

[0122] An organometallic compound having the chemical formula C was dissolved in 4-methyl-2-pentanol at a concentration of 1% by weight, and then filtered through a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare a photoresist composition.

[0123] Chemical formula C

[0124]

[0125] The prepared photoresist (PR) composition containing organometallic material was spin-coated onto an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 160°C for 60 seconds to produce the coated wafer.

[0126] The developer compositions according to Examples 1 to 11 and Comparative Examples 1 to 7 were applied to the samples and developed at a rotation speed of 1,500 rpm for 30 seconds, and then cured at 240°C for 60 seconds.

[0127] After the curing process was completed, wafer defects were measured using a surface inspection device (e.g., SurfScan SP2, KLA Tencor Corp.).

[0128] Regarding the number of defects smaller than or equal to 0.3 μm, if the number of defects is less than 150, it is given as "Good", but if the number of defects is greater than or equal to 150, it is given as "Bad".

[0129] Table 2

[0130]

[0131] Referring to Table 2, compared with the developer compositions for metal-containing photoresists according to Comparative Examples 1 to 7, the developer compositions for metal-containing photoresists according to Examples 1 to 11 exhibit excellent or suitable solubility characteristics in the non-exposed areas when applied.

[0132] The patterning apparatus, developer composition manufacturing apparatus, and / or any other related apparatus or component according to one or more embodiments of the invention described herein can be implemented using any suitable hardware, firmware (e.g., application-specific integrated circuits), software, or a combination of software, firmware, and hardware. For example, the one or more suitable components of the apparatus may be formed on an integrated circuit (IC) chip or on a discrete IC chip. Furthermore, the one or more suitable components of the apparatus may be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or may be formed on a substrate. Additionally, the one or more suitable components of the apparatus may be a process or thread running on one or more processors in one or more computing devices, the process or thread executing computer program instructions and interacting with other system components to perform the one or more suitable functions described herein. The computer program instructions may be stored in a memory, which may be implemented in a computing device using standard memory devices (e.g., for example, random access memory (RAM)). Computer program instructions may also be stored in other non-transitory computer-readable media (e.g., compact disc read-only memory (CD-ROM), flash memory drives, and / or similar devices). Furthermore, those skilled in the art will recognize that, without departing from the scope of this disclosure, the functionality of one or more suitable computing devices may be combined or integrated into a single computing device, or the functionality of a particular computing device may be distributed across one or more other computing devices.

[0133] 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 described herein, but can be appropriately modified and varied without departing from the spirit and scope of this disclosure. Therefore, such modified or varied embodiments may be understood without separating them from the technical concept and aspects of one or more embodiments of this disclosure, and the modified embodiments may fall within the scope of the appended claims and their equivalents.

Claims

1. A developer composition comprising: a metal compound; an organic solvent; and an additive; wherein the developer composition is applied to a metal-containing photoresist having an exposed portion and a non-exposed portion, and wherein in the non-exposed portion: a ratio of a number of hydrogen bonds between the metal compound and the organic solvent to a number of hydrogen bonds between the metal compound and the additive is greater than 0 and less than or equal to 10; and a ratio of a number of hydrogen bonds between the additive and the organic solvent to the number of hydrogen bonds between the metal compound and the additive is greater than 0 and less than or equal to 5, wherein the number of hydrogen bonds is determined by averaging the number of hydrogen bonds per frame during a molecular dynamics simulation; and wherein the developer composition is a developer composition for the metal-containing photoresist.

2. The developer composition of claim 1, wherein the ratio of the number of hydrogen bonds between the metal compound and the organic solvent to the number of hydrogen bonds between the metal compound and the additive in the metal-containing photoresist is greater than 0 and less than or equal to 4.

3. The developer composition of claim 1, wherein the ratio of the number of hydrogen bonds between the metal compound and the organic solvent to the number of hydrogen bonds between the metal compound and the additive in the metal-containing photoresist is in a range of 0.2 to 4.

4. The developer composition of claim 1, wherein the ratio of the number of hydrogen bonds between the additive and the organic solvent to the number of hydrogen bonds between the metal compound and the additive in the metal-containing photoresist is greater than 0 and less than or equal to 5.

5. The developer composition of claim 1, wherein a number of molecules of the metal compound having a maximum intermolecular distance of less than or equal to 3.5 A is greater than 0 and less than or equal to 10, and wherein the number of molecules is determined by averaging the count per frame during the molecular dynamics simulation.

6. The developer composition of claim 1, wherein a number of molecules of the metal compound having a maximum intermolecular distance of less than or equal to 3.5 A is greater than or equal to 5 and less than or equal to 10.

7. The developer composition of claim 1, wherein the metal compound comprises at least one metal selected from Sn, Te, Sb, and combinations thereof.

8. The developer composition of claim 1, wherein the metal compound comprises Sn.

9. The developer composition of claim 1, wherein the organic solvent comprises at least one selected from an ether, an alcohol, a glycol ether, an aromatic hydrocarbon compound, a ketone, an ester, and combinations thereof.

10. The developer composition of claim 1, wherein the organic solvent comprises at least one selected from n-butyl acetate, propylene glycol methyl ether acetate, methyl isobutyl carbinol, and combinations thereof.

11. The developer composition of claim 1, wherein the additive comprises at least one selected from an organic acid, a phosphoric acid, a phosphorous acid, a glycol compound, a diketone compound, and combinations thereof.

12. The developer composition of claim 11, wherein the additive comprises at least one selected from the group consisting of propionic acid, succinic acid, fumaric acid, acetylacetone, trifluoroacetylacetone, methylphosphonic acid, maltol, phosphorous acid, tropolone, catechol, and combinations thereof.

13. The developer composition of claim 1, wherein the additive further comprises at least one other additive selected from the group consisting of surfactants, dispersants, hygroscopic agents, coupling agents, and combinations thereof.

14. The developer composition of claim 1, wherein the number of hydrogen bonds is determined based on the molecular dynamics simulation performed under the following conditions: a molecular dynamics program including Desmond module of Materials Science Suite; a force field including Enhanced Optimized Potentials Liquid Simulations version 3; and simulation conditions including an equal number of particles-equal pressure-equal temperature ensemble, a simulation time of 50 nanoseconds, a temperature of 300 K, and a pressure of 1 atmosphere.

15. A method of forming a pattern, comprising: coating a metal-containing photoresist composition on a substrate; performing a heat treatment to form a metal-containing photoresist film on the substrate by drying and heating; exposing the metal-containing photoresist film; and developing the exposed metal-containing photoresist film with the developer composition of any one of claims 1 to 14.

16. The method of claim 15, further comprising performing a second heat treatment after the exposing the metal-containing photoresist film and before the developing the exposed metal-containing photoresist film with the developer composition, wherein the second heat treatment is performed at a temperature in a range of 90 °C to 200 °C.

17. The method of claim 15, wherein: the performing the heat treatment is performed at a temperature of 80 °C to 120 °C.

18. The method of claim 15, wherein the metal-containing photoresist composition comprises at least one tin-based compound selected from the group consisting of alkyl tin oxy, alkyl tin carboxyl, alkyl tin hydroxyl, and combinations thereof.

19. The method of claim 15, wherein the pattern formed has a half-pitch less than or equal to 20 nm and a line edge roughness less than or equal to 3 nm.

20. The method of claim 15, wherein the number of hydrogen bonds used to evaluate the developer composition is determined based on a molecular dynamics simulation performed under the following conditions: a molecular dynamics program including Desmond module of Materials Science Suite; a force field including Enhanced Optimized Potentials Liquid Simulations version 3; and simulation conditions including an equal number of particles-equal pressure-equal temperature ensemble, a simulation time of 50 nanoseconds, a temperature of 300 K, and a pressure of 1 atmosphere.

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