Developer composition containing metal photoresist and method including developing step using same

Abstract

The invention provides a developer composition for a metal-containing photoresist and a method of forming a pattern including a developing step using the developer composition. The developer composition for a metal-containing photoresist can be applied to a metal-containing photoresist having an exposed portion and an unexposed portion, and includes an organic solvent and an additive, in which the exposed portion includes a metal-oxygen-metal bonded metal oxide, and the metal oxide is substituted at a terminal end with a hydroxyl group, in the exposed portion, the metal oxide is not substituted at a terminal end with a hydroxyl group. The ratio of the number of hydrogen bonds between the metal oxide including the metal-oxygen-metal bond and the organic solvent to the number of hydrogen bonds between the metal oxide including the metal-oxygen-metal bond and the additive is greater than 0 and less than or equal to 4.5.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0121007, filed on September 5, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to a developer composition for a metal-containing photoresist and a method for forming a pattern including a development step (e.g., action or task) using the developer composition. Background Technology

[0004] In recent years, the semiconductor industry has experienced a continuous reduction in critical dimensions. This trend has driven the demand for or desire for new high-performance photoresist materials and advanced patterning methods that can support the fabrication of photoresist materials and the patterning methods that support increasingly smaller features.

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

[0006] Therefore, there is a need or desire to provide photoresist materials that improve etch impedance and resolution while simultaneously enhancing sensitivity, critical size (CD) uniformity, and LER properties in lithography processes. Summary of the Invention

[0007] One or more aspects of the embodiments disclosed herein are for developer compositions used with metal-containing photoresists.

[0008] One or more aspects of the embodiments disclosed herein are for a patterning method including a development step (e.g., action or task) utilizing the 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] A developer composition for a metal-containing photoresist according to one or more embodiments is a developer composition applied to a metal-containing photoresist having an exposed portion and an unexposed portion, and includes an organic solvent and an additive,

[0011] wherein the exposed portion includes a metal oxide containing a metal-oxygen-metal linkage, and the metal oxide is terminally substituted with a hydroxyl group (e.g., a metal oxide unit at the end of the metal oxide is substituted with a hydroxyl group),

[0012] a ratio of a number of hydrogen bonds between the metal oxide containing a metal-oxygen-metal linkage and the organic solvent to a number of hydrogen bonds between the metal oxide containing a metal-oxygen-metal linkage and the additive in the exposed portion is greater than 0 and less than or equal to 4.5,

[0013] a maximum probability distribution of the additive within about 5 angstroms of the hydroxyl group at the end of the metal oxide is greater than 0 and less than or equal to about 4,

[0014] the number of hydrogen bonds is calculated by counting the number of hydrogen bonds for each frame after a molecular dynamics simulation and taking an average of the number of hydrogen bonds for each frame (e.g., the number of hydrogen bonds is determined by averaging the number of hydrogen bonds for each frame during a molecular dynamics simulation), and

[0015] the number of molecules is calculated using a radial distribution function:

[0016] a molecular dynamics program: Materials Science Suites, Desmond module,

[0017] a force field applied for the calculation: OPLS3e, and

[0018] simulation conditions: NVT simulation, 100 nanoseconds, 500 K, 1 atmosphere.

[0019] For example, the number of hydrogen bonds is determined by performing a molecular dynamics simulation and averaging the number of hydrogen bonds for each frame during the simulation. The number of molecules is calculated using a radial distribution function. The molecular dynamics simulation is performed using Materials Science Suites, Desmond module. The force field applied in the simulation is OPLS3e. The simulation conditions include an NVT ensemble, a duration of 100 nanoseconds, a temperature of 500 K, and a pressure of 1 atmosphere.

[0020] A method of forming a pattern according to one or more embodiments includes 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 with a developer composition for a metal-containing photoresist.

[0021] A developer composition for a metal-containing photoresist according to one or more embodiments can have improved or optimized elements for a developer composition capable of minimizing or reducing solubility of a photoresist in an exposed portion, and by applying a developer composition satisfying these elements, a photoresist pattern having minimized or reduced pattern collapse in an exposed portion can be achieved.

[0022] For example, a developer composition for a metal-containing photoresist can be formulated with enhanced components selected based on molecular simulation data. These components can be designed to minimize or reduce solubility of a photoresist in an exposed portion during development. By controlling the spatial distribution of hydrogen bonding and additives to adjust the interaction between the developer and the metal oxide structure, the composition can effectively or suitably inhibit or reduce dissolution in the exposed area. This selective development behavior can help form well-defined patterns with reduced risk of pattern collapse. Such improvements are advantageous or beneficial in advanced lithography processes, including extreme ultraviolet (EUV) lithography, where high resolution patterning and dimensional stability are important. The ability to design a developer composition at the molecular level enables enhanced control over development contrast, critical dimension (CD) uniformity, and line edge roughness (LER), thereby supporting the fabrication of next-generation semiconductor devices with increasingly smaller feature sizes. BRIEF DESCRIPTION OF DRAWINGS

[0023] The accompanying drawings, together with the specification, illustrate embodiments of the present disclosure and, along with the description, serve to explain the principles of embodiments of the present disclosure.

[0024] Figures 1A-1C Cross-sectional views of process sequences are provided in order to describe a method of forming a pattern.

[0025] Figure 2 A schematic diagram illustrating the entire composition distribution of placing a metal oxide, an organic solvent, and an additive in an exposed portion for molecular dynamics calculation according to one or more embodiments of the present disclosure.

[0026] Figure 3 A schematic diagram illustrating the entire composition distribution of placing a metal oxide, an organic solvent, and an additive in an exposed portion according to Figure 2 A model schematic diagram of a composition inducing distribution of an additive and an organic solvent on a metal oxide surface.

[0027] Figure 4 A schematic diagram illustrating the composition distribution reaching an equilibrium state by performing a molecular dynamics simulation on a composition according to Figure 3 ​

[0028] BRIEF DESCRIPTION OF DRAWINGS

[0029] 100: substrate

[0030] 110: feature layer

[0031] 110P: feature pattern

[0032] 130P: photoresist pattern

[0033] OP: opening DETAILED DESCRIPTION

[0034] The subject disclosure will now be described in greater detail in connection with various embodiments thereof. It should be understood that certain features, structures, or processes, which are well known in the art, are not necessarily described or illustrated in detail herein in order to avoid obscuring the subject disclosure.

[0035] The use of “may” in describing embodiments of the disclosure indicates that one or more embodiments of the disclosure.

[0036] In this document, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Singular expressions include plural expressions unless the context clearly dictates otherwise.

[0037] As used herein, the term “and / or” or “or” includes any and all combinations of one or more of the associated listed items.

[0038] Throughout this disclosure the expression such as “at least one of,” “one or more of,” and “at least one selected from the group consisting of” when preceding the list of elements, modifies the entire list of elements and does not modify the individual elements of the list. For example, “at least one of a, b, or c” “at least one selected from the group consisting of a, b, and c” “at least one selected from the group consisting of a to c,” and / or the like, indicates only a, only b, only c, both a and b (e.g., at the same time), both a and c (e.g., at the same time), both b and c (e.g., at the same time), all of a, b, and c, or variations thereof.

[0039] 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.

[0040] In the context of this application and unless otherwise defined, the terms “use,” “using,” and “used” may be regarded as synonyms with the terms “utilize,” “utilizing,” and “utilized,” respectively.

[0041] 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 deviations in measured or calculated values ​​that would be recognized by a person skilled in the art. As used herein, “about” includes the stated value and refers to a specific value within an acceptable deviation range determined by a person skilled in the art, taking into account the measurement in question and 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 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 variations that are not substantial or 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 a person skilled in the art, and elements (e.g., claim elements) should be interpreted accordingly to cover such equivalents.

[0042] Any numerical range described herein is intended to include all subranges containing the same numerical precision within the described range. For example, the range “1.0 to 10.0” is intended to include all subranges between (and including) the described minimum value of 1.0 and the described 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.

[0043] For clarity of illustration, descriptions and relationships may not be provided, and substantially identical or similar configuration components may be designated by the same reference numerals throughout the disclosure. Furthermore, since the dimensions and thicknesses of each configuration illustrated in the figures are arbitrarily shown for better understanding and ease of description, embodiments of this disclosure are not necessarily limited thereto.

[0044] In the accompanying drawings, the thickness of layers, films, panels, areas, etc., can be magnified for clarity. The thickness of a portion of the layer, area, etc., can be magnified in the accompanying drawings for better understanding and easier description.

[0045] 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.

[0046] The following describes in more detail a metal-containing photoresist developer composition according to one or more embodiments.

[0047] According to one or more embodiments, a metal-containing photoresist developer composition may be a developer composition applied to a metal-containing photoresist having exposed and unexposed portions, and may include organic solvents and additives.

[0048] The exposed portion may include a metal oxide containing a metal-oxygen-metal bond, and the metal oxide may be terminally substituted with a hydroxyl group (e.g., the metal oxide unit at the end of the metal oxide may be substituted with a hydroxyl group).

[0049] In the exposed portion, the ratio of the number of hydrogen bonds between the metal oxide containing metal-oxygen-metal bonds and the organic solvent to the number of hydrogen bonds between the metal oxide containing metal-oxygen-metal bonds and the additive can be greater than 0 and less than or equal to about 4.5.

[0050] The maximum probability distribution of additives with their centroid within approximately 5 Å of the terminal metal oxide hydroxyl group can be greater than 0 and less than or equal to approximately 4.

[0051] The number of hydrogen bonds can be calculated by counting each frame after a kinetic simulation and taking the average of the results for each frame (e.g., the number of hydrogen bonds can be determined by averaging the number of hydrogen bonds in each frame during the kinetic simulation).

[0052] The number of molecules can be calculated using the radial distribution function:

[0053] Dynamics simulation program: Materials Science Suite, Desmond module

[0054] The force field applied to the calculation: OPLS3e (OPLS3e refers to the version of the Optimized Potentials for Liquid Simulations (OPLS) force field. It can be used in dynamical simulations to simulate molecular behavior by calculating the system's potential energy based on atomic interactions), and

[0055] Simulation conditions: NVT simulation, 100 nanoseconds, 500 K, 1 atmosphere (NPT simulation refers to a type of dynamic simulation that maintains constant temperature: N: number of particles (atoms or molecules); P: pressure; and T: temperature. This is also known as an isothermal-isobaric ensemble).

[0056] This hydrogen bond analysis provides a molecular-level understanding of how developer components interact with photoresist components, for example, in unexposed 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. The higher number of hydrogen bonds between metal compounds and organic solvents, compared to additives, promotes dissolution of unexposed portions without adversely affecting exposed areas. This selective interaction is crucial for achieving high-resolution patterning, minimizing or reducing line edge roughness, and ensuring uniform critical dimensions in advanced lithography processes.

[0057] For example, the ratio of the number of hydrogen bonds between the metal oxide containing metal-oxygen-metal bonds and the organic solvent to the number of hydrogen bonds between the metal oxide containing metal-oxygen-metal bonds and the additive can be from about 0.1 to about 4.5.

[0058] For example, the ratio of the number of hydrogen bonds between the metal oxide containing metal-oxygen-metal bonds and the organic solvent to the number of hydrogen bonds between the metal oxide containing metal-oxygen-metal bonds and the additive can be from about 0.3 to about 4.5.

[0059] For example, the maximum probability distribution of additives with a centroid within a range of about 5 angstroms from the terminal hydroxyl group of the metal oxide can be from about 0.5 to about 3.

[0060] In one or more embodiments, the lower the interaction between the metal oxide, including the metal-oxygen-metal bond, and the additive and organic solvent, and the lower the proportion of additive distributed on the surface of the metal oxide with terminal hydroxyl-substituted, the lower the solubility of the exposed portion, thereby preventing pattern collapse (or reducing the degree or occurrence of pattern collapse).

[0061] For example, the metal oxide may include at least one metal selected from tin, tellurium and antimony.

[0062] For example, metal oxides may include networks containing SnOx (where x is an integer greater than 0).

[0063] According to one or more embodiments, examples of organic solvents included in developer compositions for metal-containing photoresists may include at least one selected from ethers, alcohols, glycol ethers, aromatic hydrocarbon compounds, ketones, and esters, but the embodiments disclosed herein 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, 4-methyl-2-pentanol (or methyl isobutyl methanol (MIBC)), hexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, methyl ether ... Benzene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, 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, propyl 1-methoxy-2-acetate, methyl methoxypropionate, ethyl ethoxypropionate, or combinations thereof, but the embodiments disclosed herein are not limited thereto.

[0064] According to one or more embodiments, examples of additives included in developer compositions for use with metal photoresists may include organic acids, phosphoric acid, phosphorous acid, diol compounds and diketone compounds, but the embodiments disclosed herein are not limited thereto.

[0065] According to one or more embodiments, the developer composition for metal-containing photoresists may further include at least one other additive selected from surfactants, dispersants, hygroscopic agents and coupling agents.

[0066] In one or more embodiments, the 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 photoresist pattern.

[0067] According to one or more embodiments, a method for forming a pattern 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 (e.g., substantially uniform) layer of 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., action or task) during which the coated substrate is heated to remove residual solvents and promote adhesion of the photoresist film to the substrate surface. Once the film has stabilized (formed), it may be exposed to a radiation source (such as extreme ultraviolet, electron beam, and / or deep ultraviolet) via a photomask or direct-write system to define the desired pattern. The exposed areas may undergo chemical transformations (such as crosslinking), which alter their solubility. The substrate may then undergo a development step (e.g., action or task) using a developer composition as described in one or more embodiments, which selectively dissolves unexposed areas of the photoresist, thereby revealing patterned features with high fidelity.

[0068] For example, patterning using a metal-containing photoresist composition may include coating a metal-containing photoresist composition onto a substrate on which a thin film has been formed by spin coating, slot coating, inkjet printing, and / or similar methods, and drying the coated metal-containing photoresist composition to form a photoresist layer. The metal-containing photoresist composition may include a tin-based compound, for example, the tin-based compound may include at least one of alkyl tin oxo group, alkyl tin carboxyl group, and alkyl tin hydroxyl group.

[0069] Subsequently, a first thermal treatment process can be performed to heat the substrate on which the metal-containing photoresist film is formed. The first thermal treatment process can be performed at a temperature of approximately 80°C to approximately 120°C. In this process, the solvent is evaporated and the metal-containing photoresist film can adhere more firmly or appropriately to the substrate. For example, this first thermal treatment may also be referred to as soft baking or pre-baking and can serve one or more suitable functions in the patterning process. It can promote the controlled evaporation of residual solvent in the coated photoresist layer to achieve a uniform (e.g., substantially uniform) film thickness and prevent / reduce defects (such as blistering and / or delamination) during subsequent processing. Furthermore, this thermal step (e.g., function or task) can promote partial densification of the metal-containing photoresist, enhancing its mechanical stability and adhesion to the underlying substrate. The selected temperature range of approximately 80°C to approximately 120°C can be used to ensure sufficient or appropriate solvent removal without triggering premature chemical reactions or degradation of the photoresist components. This step (e.g., function or task) can be used to ensure consistent exposure and development performance in subsequent stages of the lithography process.

[0070] Then, the photoresist film can be selectively exposed.

[0071] 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) and / or similar, as well as other sources, such as electron beams (e-beam) and / or similar.

[0072] For example, the light used for exposure according to one or more embodiments may be light having a wavelength range of about 5 nanometers to about 150 nanometers, such as extreme ultraviolet light (EUV, wavelength 13.5 nanometers) and / or similar, as well as other sources such as electron beams (e-beams).

[0073] In the step (e.g., action or task) of forming a photoresist pattern, a negative (type) pattern can be formed.

[0074] The exposed portions of a photoresist film can be cross-linked (such as condensation between organometallic compounds) to form polymers containing metal oxides with metal-oxygen-metal bonds, thus having a different solubility than the unexposed portions of the photoresist film.

[0075] 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 following the exposure of the metal-containing photoresist film (e.g., a function or task). This thermal process can be performed at temperatures ranging from approximately 90°C to approximately 200°C, depending on the specific formulation of the photoresist and the desired patterning result. The primary function of PEB can be to promote chemical reactions, such as crosslinking and / or condensation, within the exposed areas of the photoresist. These reactions can enhance structural integrity and reduce solubility in the exposed areas, thereby enabling the formation of negative tone patterns during development. Increased temperatures can accelerate the mobility of reactive species 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 achieve high-resolution features, minimize / reduce line edge roughness (LER), and ensure consistent critical dimension (CD) control across the substrate.

[0076] By performing a second heat treatment process, the exposed portions of the photoresist film become less soluble in the developer.

[0077] For example, a photoresist pattern corresponding to a negative (genre) tone image can be achieved by dissolving and then removing the photoresist film corresponding to the unexposed portion using a photoresist developer as described in one or more embodiments.

[0078] As described in one or more embodiments, the photoresist pattern formed can have a thickness width 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 light (EUV; wavelength 13.5 nm) and / or the like, as well as other sources with high energy, such as electron beams. For example, the photoresist pattern can be formed to have a thickness width 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.

[0079] In contrast, the photoresist pattern may have a 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.

[0080] The methods described herein can leverage custom hydrogen-bonded interactions of developer compositions to achieve high-resolution patterning in metal-containing photoresists. By selectively dissolving unexposed regions while preserving the integrity of exposed, cross-linked regions, developer compositions enable precise pattern transfer with minimal or reduced line-edge roughness (LER) and excellent or suitable critical dimension (CD) control. This could be advantageous or beneficial for next-generation lithography technologies such as EUV and electron beam lithography, where sub-20 nm features and tight process windows are required or desired. The ability to form patterns with half-pitch values ​​below approximately 30 nm and LER values ​​below approximately 3 nm demonstrates the effectiveness of developer compositions in supporting advanced semiconductor manufacturing nodes.

[0081] The method of forming the pattern is described in more detail below with reference to the accompanying drawings.

[0082] Figures 1A-1C A cross-sectional view is provided to illustrate the process sequence in order to describe the patterning method.

[0083] Reference Figure 1A The exposed photoresist film can be developed to form a photoresist pattern 130P.

[0084] In one or more embodiments, the exposed photoresist film can be developed to remove unexposed portions of the photoresist film, and a photoresist pattern 130P including the exposed portions of the photoresist film can be formed. The photoresist pattern 130P may include a plurality of openings OP.

[0085] 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 photoresists according to one or more embodiments may be used as a developer composition.

[0086] Reference Figure 1B 130P photoresist patterns can be used for processing Figure 1A Feature layer 110 in the obtained product.

[0087] For example, feature layer 110 can be etched through an opening OP of photoresist pattern 130P, feature layer 110 exposed by one or more suitable processes, impurity ions can be implanted into feature layer 110, an additional film can be formed on feature layer 110 through opening OP, a portion of feature layer 110 can be deformed through opening OP, and / or the like. Figure 1B An example process is shown for processing the feature pattern 110P by etching the feature layer 110 exposed through the opening OP.

[0088] Reference Figure 1C ,exist Figure 2The photoresist pattern 130P remaining on the feature pattern 110P can be removed from the resulting material. To remove the photoresist pattern 130P, an ashing and stripping process can be used. The feature pattern 110P is located on the substrate 100.

[0089] Hereinafter, one or more embodiments of the present disclosure will be described in more detail through examples relating to the preparation of developer compositions for metal-containing photoresists according to one or more embodiments. However, the embodiments of the present disclosure are not limited to the following examples.

[0090] The molecular dynamics simulation results are shown in Table 1.

[0091] For molecular dynamics calculations, the Materials Science Suites program and the Desmond module were used to generate an initial composition including organic solvents and additives. The amounts of additives and solvents were adjusted according to the additive conditions so that the total number of additive and organic solvent molecules was 2000.

[0092] In one or more embodiments, the metal oxide may be SnO for molecular dynamics simulations. x Simulated structure of the crystal (where x is an integer greater than 0). Due to the limitations of molecular dynamics calculations for SnO... x Since crystalline molecules are not feasible due to the extended coordination number of Sn atoms, molecular dynamics-enabled SnO has been created by replacing Si atoms with Sn atoms based on the cubic structure of SiO2 presented in the reference. x Crystal structure: MD Foster, OD Friedrichs, RG Bell, FAA Paz, and J. Klinowski, “Chemical evaluation of hypothetical uninodalzeolites,” Journal of the American Chemical Society, 126: 9769–9775, 2004, the entire contents of which are incorporated herein by reference.

[0093] The schematic diagram of the components whose initial composition has reached equilibrium is shown in this article. Figure 2 and Figure 3 middle.

[0094] Figure 2 This is a schematic diagram illustrating the distribution of the entire composition of metal oxides, organic solvents, and additives in an exposed portion used for molecular dynamics calculations according to one or more embodiments of this specification.

[0095] Figure 3 According to Figure 2A schematic diagram of a model that induces additives and organic solvents to distribute onto the surface of a metal oxide.

[0096] Reference Figure 2 In the initial composition of the exposed portion, additive (A) and organic solvent (B) are randomly arranged in SnO. x In the crystal (C) structure, and

[0097] exist Figure 3 In the middle, SnO x The crystal is induced to the surface (D) by using a barrier potential.

[0098] Next, molecular dynamics simulations were performed for 100 ns using the NVT ensemble method (thermostat method: Nose-Hoover chain), at 1 atm and 500 K, to calculate the equilibrium state. At this point, the compositional distribution at equilibrium is shown in... Figure 4 middle.

[0099] Reference Figure 4 In the composition after optimization of the exposed portion, in the induction to SnO x SnO on the surface of a crystal (C) structure x (D) Maintain a specific (e.g., set or predetermined) distance level between the organic solvent (B) and the additive (A) such that (e.g., so that) the dissolution of the developer is inhibited or reduced.

[0100] In one or more embodiments, the number of hydrogen bonds is calculated by counting the number of hydrogen bonds between metal oxides, organic solvents and additives in the entire cell frame by frame after molecular dynamics simulation and taking the average of the values ​​of each frame.

[0101] In addition, SnO x The number of additive molecules on the surface (additive distribution) is calculated using a radial distribution function, which is the distribution of the additive centroid at a distance from SnO. x The probability of the terminal surface hydroxyl group being within approximately 5 Å.

[0102] Table 1

[0103]

[0104] additive

[0105] C1: Propionic acid

[0106] C2: Succinic acid

[0107] C3: Fumaric acid

[0108] C4: Acetyl acetone

[0109] C5: Trifluoroacetylacetone

[0110] C6: Methylphosphonic acid

[0111] C7: Maltol

[0112] C8: Phosphorous acid

[0113] C9: Tropolone

[0114] C10: Catechol

[0115] organic solvents

[0116] S1: n-Butyl acetate

[0117] S2: Propylene glycol monomethyl ether acetate (PGMEA)

[0118] S3: Methyl isobutyl methanol (MIBC)

[0119] Evaluation: ArF pattern evaluation

[0120] An organometallic compound having the following chemical formula C structure was dissolved in 4-methyl-2-pentanol at a concentration of 1% by weight, and then filtered through a 0.1-micron polytetrafluoroethylene (PTFE) syringe filter to prepare a photoresist composition.

[0121] Chemical formula C

[0122]

[0123] The prepared organometallic photoresist (PR) composition was spin-coated on an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 110°C for 60 seconds to produce a coated wafer.

[0124] Using an ArF immersion exposure apparatus (Nikon Precision Inc.; NSR-S610C, NA=1.30, σ0.98 / 0.65, 35° dipole s-polarized illumination, 6% halftone phase-shift mask), coated wafers were exposed to 20 to 35 mJ in an L / S pattern, baked at 100°C (PEB) for 60 seconds, developed at 1500 rpm for 30 seconds using the developer compositions according to Examples 1 to 5 and Comparative Examples 1 to 11, and cured at 240°C for 60 seconds to obtain a 1:1 line-to-spacing (L / S) pattern with a width of 40 nm. The cross-sectional shape of this pattern was examined using an electron microscope. The pattern collapse rate was calculated according to Equation 1 to evaluate the ArF pattern performance.

[0125] Equation 1

[0126] Pattern collapse rate = {(number of collapsed patterns) / (total number of patterns)} * 100 (%)

[0127] Evaluation Criteria

[0128] ○: Pattern collapse incidence rate < 60%

[0129] X: Pattern collapse rate ≥ 60%

[0130] Table 2

[0131]

[0132] Referring to Table 2, when the metal-containing photoresist developer compositions according to Examples 1 to 5 are applied, compared with the metal-containing photoresist developer compositions according to Comparative Examples 1 to 11, the dissolution ability in the exposed portion is suppressed or reduced, and the pattern collapse is minimized or reduced.

[0133] The patterning apparatus, developer composition manufacturing apparatus, and / or any other related apparatus or component described herein according to one or more embodiments of this disclosure may be implemented using any suitable hardware, firmware (e.g., application-specific integrated circuit), software, or a combination of software, firmware, and hardware. For example, one or more suitable components of the apparatus may be formed or configured on an integrated circuit (IC) chip or on a discrete IC chip. Furthermore, 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 formed or configured on a substrate. Additionally, one or more suitable components of the apparatus may be a program or thread running on one or more processors, in one or more computing devices, executing computer program instructions and interacting with other system components to perform one or more suitable functions as described herein. The computer program instructions may be stored in memory, which may be implemented in the computing device using standard memory devices, such as random access memory (RAM). The computer program instructions may also be stored on other non-transitory computer-readable media, such as CD-ROMs, flash drives, and / or the like. Furthermore, those skilled in the art will recognize that the functions of one or more suitable computing devices can be combined or integrated into a single computing device, or that the functions of a particular computing device can be distributed across one or more other computing devices without departing from the scope of this disclosure.

[0134] 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 suitable 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 disclosed herein, and the modified embodiments are within the scope of the claims appended to this disclosure and their equivalents.

Claims

1. A developer composition comprising: an organic solvent; and an additive, wherein: the developer composition is applied to a metal-containing photoresist having an exposed portion and an unexposed portion; the exposed portion comprises a metal oxide, the metal oxide comprising a metal-oxygen-metal linkage; and a metal oxide unit at an end of the metal oxide is substituted with a hydroxyl group, wherein, in the exposed portion: a ratio of a number of hydrogen bonds between the metal oxide comprising the metal-oxygen-metal linkage and the organic solvent to a number of hydrogen bonds between the metal oxide comprising the metal-oxygen-metal linkage and the additive is greater than 0 and less than or equal to 4.5; a maximum probability distribution of a center of mass of the additive within 5 A of the hydroxyl group at the end of the metal oxide is greater than 0 and less than or equal to 4; and the number of hydrogen bonds is determined by averaging the number of hydrogen bonds for each frame during a molecular dynamics simulation, and wherein the developer composition is a developer composition for a metal-containing photoresist.

2. The developer composition of claim 1, wherein: the ratio of the number of hydrogen bonds between the metal oxide comprising the metal-oxygen-metal linkage and the organic solvent to the number of hydrogen bonds between the metal oxide comprising the metal-oxygen-metal linkage and the additive is 0.1 to 4.

5.

3. The developer composition of claim 1, wherein: the ratio of the number of hydrogen bonds between the metal oxide comprising the metal-oxygen-metal linkage and the organic solvent to the number of hydrogen bonds between the metal oxide comprising the metal-oxygen-metal linkage and the additive is 0.3 to 4.

5.

4. The developer composition of claim 1, wherein: the maximum probability distribution of the center of mass of the additive within 5 A of the hydroxyl group at the end of the metal oxide is 0.5 to 3.

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

6. The developer composition of claim 1, wherein: The metal oxide includes a network comprising SnO x x is an integer greater than 0.

7. 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.

8. 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.

9. 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.

10. The developer composition of claim 1, wherein: the additive comprises at least one selected from propionic acid, succinic acid, fumaric acid, acetylacetone, trifluoroacetylacetone, methylphosphonic acid, maltol, phosphorous acid, tropolone, catechol, and combinations thereof.

11. The developer composition of claim 1, further comprising an additional additive selected from at least one of a surfactant, a dispersant, a hygroscopic agent, a coupling agent, and combinations thereof.

12. The developer composition of claim 1, wherein the number of hydrogen bonds 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 OPLS3e; and simulation conditions including NPT ensemble, 100 nanoseconds simulation time, 500 K temperature, and 1 atm pressure.

13. A method of forming a pattern, comprising: coating a metal-containing photoresist composition on a substrate; performing a thermal treatment, wherein a metal-containing photoresist film is formed on the substrate by drying and heating; exposing the metal-containing photoresist film; and developing with the developer composition of any one of claims 1 to 12.

14. The method of claim 13, further comprising performing a second thermal treatment after the exposing of the metal-containing photoresist film and before developing the exposed metal-containing photoresist film with the developer composition, wherein the second thermal treatment is performed at a temperature in a range of 90 °C to 200 °C.

15. The method of claim 13, wherein: the performing of the thermal treatment is performed at a temperature in a range of 80 °C to 120 °C.

16. The method of claim 13, wherein the metal-containing photoresist composition comprises at least one tin-based compound selected from the group consisting of an alkyl tin oxy group, an alkyl tin carboxyl group, an alkyl tin hydroxyl group, and combinations thereof.

17. The method of claim 13, wherein: the pattern has a pitch with a half-pitch less than or equal to 50 nanometers and a line width roughness less than or equal to 10 nanometers.

18. The method of claim 13, wherein: the pattern has a thickness in a range of 5 nanometers to 100 nanometers.

19. The method of claim 13, wherein: the exposing of the metal-containing photoresist film is exposing the metal-containing photoresist film to light having a wavelength in a range of 5 nanometers to 150 nanometers.

20. The method of claim 13, wherein the number of hydrogen bonds for evaluating 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 OPLS3e; and simulation conditions including NPT ensemble, 100 nanoseconds simulation time, 500 K temperature, and 1 atm pressure.

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