Method for forming a subsoil, semiconductor structure, and reactor system

Abstract

This invention provides a method for forming a base layer for lithography patterning. [Solution] The method includes providing a substrate into a reaction chamber and introducing plasma into the reaction chamber. The method also includes introducing a precursor gas into the reaction chamber, the precursor gas containing at least one carbon-carbon double bond.

Description

[Technical Field]

[0001] This disclosure generally relates to a method for forming a substrate for lithography patterning. More specifically, the embodiments of this disclosure relate to a method for forming a substrate with a precursor gas containing carbon-carbon double bonds, a semiconductor structure comprising the substrate, and a reactor system for carrying out the method. [Background technology]

[0002] In the semiconductor industry, extreme ultraviolet (EUV) lithography has emerged as an essential technology for the manufacturing of advanced devices. As feature area sizes continue to shrink, the need for precise pattern formation with high accuracy and minimal defects is becoming increasingly important. One of the challenges in EUV lithography is optimizing the underlayer material used in the patterning process. The underlayer plays a crucial role in improving lithography performance by enhancing light absorption and reducing line edge roughness (LER).

[0003] Carbon-based films are attracting attention as promising EUV underlayer materials due to their favorable optical properties and suitability for high-resolution imaging. However, achieving the optimal underlayer composition requires extensive material screening to balance multiple performance parameters such as dose requirements, film stability, and etching selectivity.

[0004] Existing approaches to EUV undercoating often suffer from a trade-off between dose efficiency and process stability. Many conventional materials require high irradiation doses to achieve adequate patterning fidelity, which can lead to higher costs and throughput limitations. Therefore, continuous development and screening of novel chemical compositions are needed to improve dose reduction and ensure stable processing conditions. This disclosure addresses the aforementioned challenges by introducing newly screened chemical formulations designed to enhance the performance of EUV undercoatings, thereby improving semiconductor manufacturing efficiency. SUMMARY OF THE INVENTION MEANS FOR SOLVING THE PROBLEMS

[0005] The present disclosure provides a method of forming an underlayer for lithographic patterning. The method includes providing a substrate in a reaction chamber. The method includes introducing plasma into the reaction chamber. The method includes introducing a precursor gas into the reaction chamber, wherein the precursor gas comprises at least one carbon-carbon double bond.

[0006] In some embodiments, the precursor gas comprises a cyclic hydrocarbon structure having at least one carbon-carbon double bond in the ring structure. In some embodiments, the precursor gas further comprises at least one branched substituent on the cyclic hydrocarbon structure. In some embodiments, the branched substituent comprises at least one carbon-carbon double bond. In some embodiments, the precursor gas comprises limonene and / or a limonene derivative.

[0007] In some embodiments, the limonene derivative comprises a limonene oxidation / epoxidation derivative. In some embodiments, the limonene oxidation / epoxidation derivative is carvone (2-methyl-5-(prop-1-en-2-yl)cyclohexa-2-en-1-one, C 10 H 14 O), carveol (2-methyl-5-(prop-1-en-2-yl)cyclohexa-2-en-1-ol, C 10 H 16 O), limonene 1,2-epoxide (1,2-epoxy-p-mentha-8-ene, C 10 H 16 O), limonene dioxide (1,2;8,9-diepoxy-p-menthane, C 10 H 16 O2), perillyl alcohol (4-(prop-1-en-2-yl)cyclohex-1-ene-1-methanol, C 10 H 16 O), perillic acid (4-(prop-1-en-2-yl)cyclohex-1-enecarboxylic acid, C 10 H14 O2), α-terpineol (p-menta-1-en-8-ol, C 10 H 18 O), Limonene hydroperoxide (4-(prop-1-en-2-yl)cyclohexa-1-en-1-yl hydroperoxide, C 10 H 16 Contains one or more of the following (O2):

[0008] In some embodiments, the limonene derivative includes limonene addition derivatives and limonene hydrogenation derivatives. In some embodiments, the limonene addition derivative and limonene hydrogenation derivative are dihydrolimonene(4-(propan-2-yl)-1-methylcyclohexa-1-ene, C 10 H 18 ), tetrahydrolimonene (p-menthane, C 10 H 20 ), dihydrocarbon (2-methyl-5-(propan-2-yl)cyclohexane-1-one, C 10 H 18 O), dihydrocarbeol (2-methyl-5-(propan-2-yl)cyclohexane-1-ol, C 10 H 20 O), Limonene hydrochloride (4-(propan-2-yl)-1-methylcyclohexa-1-yl chloride, C 10 H 17 Cl), limonene hydrobromide (4-(propan-2-yl)-1-methylcyclohexa-1-yl bromide, C 10 H 17 Br), limonene maleic anhydride adduct (2,5-dioxabicyclo[2.2.2]octane-3,6-dione derivative, C 14 H 20 O3), hydrogenated limonene polymer ([C 10 H 16 ] n ) includes one or more of the following.

[0009] In some embodiments, the limonene derivative includes limonene esterified or other functionalized derivatives. In some embodiments, the limonene esterified or other functionalized derivative is carbyl acetate (2-methyl-5-(prop-1-en-2-yl)cyclohexa-2-en-1-yl acetate, C 12 H 20 O2), Carbyl propionate (2-methyl-5-(prop-1-en-2-yl)cyclohexa-2-en-1-ylpropanoate, C 13 H 22 O2), dihydrocarbyl acetate (2-methyl-5-(propan-2-yl)cyclohexane-1-yl acetate, C 12 H 22 O2), Limonene Acrylate (4-(prop-1-en-2-yl)-1-methylcyclohexa-1-en-1-yl acrylate, C 13 H 20 O2), Limonene methacrylate (4-(propa-1-en-2-yl)-1-methylcyclohexa-1-en-1-yl 2-methylpropa-2-enoate, C 14 H 22 O2), periryl acetate (4-(prop-1-en-2-yl)cyclohexa-1-en-1-yl acetate, C 12 H 18 O2), epoxidized limonene acrylate (1,2-epoxy-4-(propa-1-en-2-yl)-1-methylcyclohexa-1-yl acrylate, ~C 13 H 20 O3), limonene carbonate (4-(propa-1-en-2-yl)-1-methyl-2-oxabicyclo[2.2.2]octan-3-one, C 10 H 16 Contains one or more of the following (O3):

[0010] In some embodiments, the underlying layer contains carbon-carbon double bonds. In some embodiments, the step of introducing the precursor gas into the reaction chamber is repeated once or multiple times. In some embodiments, the amount of precursor gas is pulsed. In some embodiments, the plasma is selected from Ar plasma, He plasma, and N2 plasma. In some embodiments, the method further includes introducing a reactive gas into the reaction chamber. In some embodiments, the reactive gas is selected from H2, O2, CO2, and NH3, and the reactive gas is continuous. In some embodiments, the method further includes purging the reaction chamber.

[0011] In some embodiments, the limonene derivative includes a monoterpene or other functionalized derivative. In some embodiments, the monoterpene derivative is pinene (C 10 H 16 ), Karen (C 10 H 16 ), Camphen (C 10 H 16 ), terpinene (C 10 H 16 ), phellandrene (C 10 H 16 ), Sabinen (C 10 H 16 ), terpinolene (C 10 H 16 ) includes one or more of the following. [Brief explanation of the drawing]

[0012] [Figure 1] This is a schematic diagram of a method for forming an underlayer on a substrate according to some embodiments of the present disclosure. [Figure 2] This is a timing sequence suitable for use in flow 100 of the method according to some embodiments of the present disclosure. [Figure 3] This is a schematic diagram of a method for forming an underlayer on a substrate according to some embodiments of the present disclosure. [Figure 4] This is a timing sequence suitable for use in flow 300 of the method according to some embodiments of the present disclosure. [Figure 5]This is a semiconductor structure according to some embodiments of the present disclosure. [Figure 6] This is a reactor system according to some embodiments of the present disclosure. [Figure 7] The characteristics of the substrate formed by the method according to some embodiments of this disclosure are shown. [Figure 8] The characteristics of the substrate formed by the method according to some embodiments of this disclosure are shown. [Modes for carrying out the invention]

[0013] The present invention can be better understood by reading the following embodiments and examples for carrying out the invention, together with the references made to the accompanying drawings.

[0014] While certain embodiments and examples are disclosed below, it will be understood by those skilled in the art that the scope of the invention extends beyond the specifically disclosed embodiments and / or uses of the invention, as well as obvious modifications and equivalents thereof. Therefore, it is not intended that the scope of the invention disclosed be limited by the specific disclosed embodiments described below.

[0015] As used herein, the term “substrate” may refer to any substrate(s), including any modified substrate(s) on which devices, circuits, or films may be formed. A “substrate” can be continuous or discontinuous, rigid or flexible, solid or porous, or a combination thereof. A substrate can be in any form, such as powder, plate, or workpiece. A substrate in plate form may include wafers of various shapes and sizes. A substrate may be made from semiconductor materials, such as silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide. In some embodiments, a substrate may have OH terminations. OH terminations can occur spontaneously, for example, through atmospheric oxidation, or they can be intentionally provided, for example, by subjecting the substrate to plasma treatment.

[0016] For example, substrates in powder form may have applications in pharmaceutical manufacturing. Porous substrates may contain polymers. Examples of workpieces may include medical devices (e.g., stents and syringes), jewelry, tooling devices, components for battery manufacturing (e.g., anodes, cathodes, or separators), or components for photovoltaic cells.

[0017] The continuous substrate may extend beyond the boundary of the process chamber in which the deposition process takes place. In some processes, the continuous substrate may move through the process chamber, thereby allowing the process to continue until the edge of the substrate is reached. The continuous substrate may be supplied from a continuous substrate supply system to enable the manufacture and production of continuous substrates in any suitable form.

[0018] Non-limiting examples of continuous substrates may include sheets, nonwoven films, rolls, foils, webs, flexible materials, continuous filaments, or bundles of fibers (e.g., ceramic or polymer fibers). Continuous substrates may also include carriers or sheets on which discontinuous substrates are placed.

[0019] The specific implementations presented and described are illustrative of the present invention and its best mode, and are not intended to limit the embodiments and scope of implementation in any way or otherwise. In fact, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the system may not be described in detail. Furthermore, the connection lines shown in various figures are intended to represent exemplary functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships or physical connections may exist in actual systems and / or may not exist in some embodiments.

[0020] The configurations and / or approaches described herein are illustrative in nature, and it should be understood that these particular embodiments or examples should not be considered limiting, as numerous variations are possible. A particular routine or method described herein may represent one or more of any number of processing strategies. Therefore, the various operations described herein may be performed in the order shown, in other orders, or, in some cases, omitted.

[0021] The subject matter of this disclosure includes all novel and non-obvious combinations and partial combinations of the various processes, systems, and configurations disclosed herein, as well as all their equivalents.

[0022] Exposure of a substrate to a precursor may result in one or more physicoadsorptions and / or chemiadsorptions of at least one of the precursor and precursor fragments on the substrate. Exposure from multiple reactant pulses may result in one or more physicoadsorptions and / or chemiadsorptions of at least one of the reactant and reactant fragments on the substrate.

[0023] The terms “first,” “second,” and so on, as used herein, may be used to describe various members, regions, layers, and / or parts, but it should be understood that these members, regions, layers, and / or parts should not be limited by these terms. The terms do not imply any particular order, vertical relationship, or priority, and are used solely to distinguish one member, region, or part from another. Accordingly, the first member, region, or part described below may refer to the second member, region, or part without departing from the teachings of this disclosure.

[0024] As used herein, "substantially" or "nearly the same" means a different value or shape, for example, ±5%, ±2%, ±1%, or ±0.5% of one or more cross-sectional dimensions of the shape. Percentages may be absolute or relative.

[0025] In the drawings, deformations from the illustrated shape should be anticipated, for example, as a result of manufacturing techniques and / or tolerances. Therefore, embodiments should not be construed as being limited to specific shapes of the regions illustrated herein, and may include, for example, deviations of shape resulting from manufacturing. Furthermore, drawings may be used to illustrate various feature parts, which may not be drawn to scale.

[0026] When preceding a list of elements, expressions like "at least one" modify the entire list of elements, not the individual elements of the list.

[0027] As used herein, “atomic layer deposition,” abbreviated as “ALD,” refers to a method of depositing a film on a substrate by sequentially exposing its surface to alternating gas-phase reactants. In contrast to chemical vapor deposition, different reactants are not present simultaneously in the reactor; rather, they are introduced as a series of consecutive, non-overlapping pulses. In each of these pulses, the reactants react with the surface in a self-limiting or substantially self-limiting manner. Furthermore, as used herein, ALD may also mean processes represented by related terms, such as chemical gas-phase atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas-source MBE, or organometallic MBE, and chemical beam epitaxy, when performed with alternating pulses of reactants. Plasma-enhanced atomic layer deposition (PEALD) refers to an ALD process in which plasma is applied during the ALD process or one or more of the subprocesses.

[0028] As used herein, "chemical vapor deposition," abbreviated as "CVD," refers to a method of depositing a film onto a substrate by exposing its surface to one or more gaseous reactants that react and / or decompose on the substrate surface to produce a desired film. Typically, CVD is carried out by introducing the reactants together into a reactor. Plasma-enhanced chemical vapor deposition (PECVD) refers to a CVD process in which plasma is applied during one or more of the CVD steps or substeps.

[0029] As used herein, "chemioadsorption" refers to an adsorption process caused by a reaction on an exposed surface that creates, for example, a covalent or ionic bond between the surface and the adsorbent.

[0030] As used herein, “film” refers to a continuous, substantially continuous, or discontinuous material that extends perpendicular to the thickness direction and covers at least a portion of a surface. Films may include two-dimensional materials, three-dimensional materials, nanoparticles, or partial or complete molecular layers, partial or complete atomic layers, or even clusters of atoms or molecules. Films may be constructed from one or more indistinguishable layers (e.g., monolayers or sub-monolayers) to produce a uniform or substantially uniform material, and the number of layers affects the thickness of the material.

[0031] As used herein, “gas” refers to a state of matter consisting of atoms or molecules that have no defined volume or shape. Gases include vaporized solids and / or liquids and may consist of a single gas or a mixture of gases, depending on the context.

[0032] As used herein, “plasma” refers to an ionized gas containing approximately equal numbers of negatively and positively charged species, generally electrons and ions. Excited and reactive species are also contained within the plasma, such as atoms and radicals, metastable atoms and molecules, and photons. Plasma discharge requires an externally applied electric or magnetic field to ionize the gas. Plasma generation schemes and geometric shapes include, but are not limited to, capacitively coupled plasmas (CCPs), inductively coupled plasmas (ICPs), and RF-hollow cathode (HC) plasmas, which differ in their generation of excited and reactive species and, as a result, can provide very different fluxes of various species.

[0033] As used herein, “precursor” means a compound that participates in a chemical reaction to form another compound or element, and a portion of the precursor (elements or groups within the precursor) is incorporated into the compound or element resulting from the chemical reaction. The compound or element resulting from the chemical reaction may be a layer and / or film formed on the surface of a substrate.

[0034] As used herein, “reactant” refers to a compound that participates in a chemical reaction to form another compound or element. In some examples, the reactant is a precursor. In other examples, the compound or element resulting from a chemical reaction does not contain any part of the reactant (an element or group within the reactant), and therefore the reactant is not a precursor.

[0035] As used herein, "self-limiting" refers to a process that proceeds through a finite process and terminates when that finite process is completed. For example, a self-limiting surface reaction terminates when the surface becomes saturated and all available and / or accessible surface reactive sites are depleted. At most, a single monolayer may be formed on the surface.

[0036] As used herein, “substituent” means an atom or group of atoms that substitutes one or more atoms (such as hydrogen atoms) or groups of atoms in a parent compound, thereby producing a new compound. The substituent replaces the original atom or group of atoms in the parent molecule. For simplicity, substituents may be represented as “R” groups in chemical formulas, and each “R” group in a compound may be independently selected unless otherwise specified. Examples of substituents, but not limited to, include hydrogen atoms (H), “alkyl groups,” e.g., saturated linear or branched C1-C13 10Hydrocarbons, preferably C1-C6 hydrocarbons (e.g., methyl, ethyl, propyl, isopropyl, butyl, i-butyl, s-butyl, t-butyl, pentyl, 3-pentyl, neopentyl, and hexyl), "cycloalkyl groups," for example, C3-C6 cyclic hydrocarbons (e.g., cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl), "alkenyl groups," for example, C2-C6 linear or branched unsaturated hydrocarbons (e.g., vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, ethinyl, propargyl, butynyl, pentynyl, and hexynyl), "allyl groups," for example, phenyl, benzyl, tolyl, xylyl, naphthyl, cyclopentadienyl, and methyl, dimethyl, or ethylcyclopentadienyl groups, hydroxyl groups (OH), "alkoxy groups," for example, linear or branched C1-C6 10 Alkoxy groups, typically C1-C4 alkoxy groups (e.g., methoxy, ethoxy, n-propoxy, i-propoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy), hydroxyalkyl groups, e.g., linear or branched C1-C4 groups. 10Hydroxyalkyl groups, typically linear or branched C1-C4 hydroxyalkyl groups (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl), "alkoxycarbonyl groups," for example, linear or branched C1-C6 carbonyl hydrocarbons (e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, and hexyloxycarbonyl), thiol groups (SH), "alkylthiol groups," for example, linear or branched C Examples include 1-C6 thiols (e.g., thiolmethyl, thiolethyl, thiolpropyl, thiolbutyl, thiolpentyl, and thiolhexyl), halides (X), e.g., fluorides (F), chlorides (Cl), bromides (Br), iodides (I), and "haloalkyl groups," e.g., linear or branched C1-C6 alkyl halides having one or more halogen atoms (e.g., iodomethyl, bromomethyl, chloromethyl, fluoromethyl, trifluoromethyl, 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl). Substituents may be substituted themselves. For example, a hydroxyalkyl group is a substituted alkyl group in which the H atom on the alkyl group is substituted with an OH group.

[0037] The terms "one or more" and "at least one" are interchangeable in this specification. It should also be noted that the terms "including" and "having" are interchangeable.

[0038] The term "approximately" generally refers to a range of numbers that are considered equivalent to a given set of values ​​(e.g., having the same function or result). In some cases, the term "approximately" may include numbers rounded to the nearest significant figure.

[0039] When applied to compositions, methods, or systems, the term “essentially” generally means that the additional components do not substantially alter the properties and / or functions of the composition, method, or system.

[0040] Where applied to compositions, methods, or systems, the term “substantially” generally refers to a percentage of a value, characteristic, feature, etc., that is at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, at least about 98%, at least about 99%, at least about 99.5%, at least about 99.9%, or more, or any percentage between about 70% and about 100%, or conversely, the absence of such values, characteristics, features, etc. In some embodiments, the term “substantially” means a percentage of about 90%, about 95%, about 97%, about 98%, about 99%, about 99.5%, or about 99.9%.

[0041] "At least one," "one or more," and "and / or" are open-ended expressions that function as both conjunctions and disjunctions. For example, the expressions "at least one of A, B, and C," "at least one of A, B, or C," "one or more of A, B, and C," and "one or more of A, B, or C," as well as "A, B, and / or C," mean A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C. Each of A, B, and C in the above expressions may be an element such as X, Y, and Z, or X1-X n Y1-Y m , and Z1-Z o When referring to classes of elements such as X, Y, and Z, the phrase can refer to a single element selected from X, Y, and Z, a combination of elements selected from the same class (e.g., X1 and X2), and a combination of elements selected from two or more classes (e.g., Y1 and Z). O It is intended to refer to )

[0042] All numerical ranges described throughout this disclosure include upper and lower limits, and it should be understood that any narrower numerical ranges that fall within such broad numerical ranges are also deemed to be as if they were all explicitly described herein. For example, the phrases “about 2 to about 4” or “2 to 4” include 2 and 4, and whole numbers and / or integers are in the range of about 2 to about 3, about 3 to about 4, and each possible range is based on real numbers (e.g., irrational and / or rational numbers), such as about 2.1 to about 3.9, about 2.1 to about 3.4, etc.

[0043] This disclosure generally relates to methods for forming a substrate on a substrate using CVD (e.g., PECVD) or ALD (e.g., PEALD), semiconductor structures having a substrate, and reactor systems for carrying out the methods, and more particularly to the use of a precursor gas having at least one carbon-carbon double bond for forming a substrate having a carbon-carbon double bond in order to provide dose reduction for EUV lithography. Various embodiments of the methods and systems, and the benefits derived therefrom, are described below.

[0044] Moving on to the figures, Figure 1 is a schematic diagram of flow 100 of a method for forming a substrate on a substrate according to some embodiments of the present disclosure. Step 110 includes providing the substrate in a reaction chamber. Next, step 120 involves introducing a sealing gas into the reaction chamber. Next, step 130 involves introducing plasma into the reaction chamber. Next, step 140 involves introducing a reactive gas into the reaction chamber. Next, step 150 involves introducing a precursor gas into the reaction chamber. Next, step 150 involves purging the reaction chamber. Flow 100 of the method also includes cycle 170. Cycle 170 includes steps 150 and 160. Cycle 170 is repeated once or more times (e.g., several times) until the desired substrate is formed.

[0045] In some embodiments, the precursor gas comprises a cyclic hydrocarbon structure having at least one carbon-carbon double bond within the ring structure.

[0046] In some embodiments, the precursor gas comprises a cyclic hydrocarbon structure having at least one branched substituent on a cyclic hydrocarbon structure having at least one carbon-carbon double bond within a ring structure.

[0047] In some embodiments, the precursor gas comprises a cyclic hydrocarbon structure having at least one branched substituent on the cyclic hydrocarbon structure, the branched substituent comprising at least one carbon-carbon double bond.

[0048] In some embodiments, the precursor gas comprises a cyclic hydrocarbon structure having at least one branched substituent on a cyclic hydrocarbon structure having at least one carbon-carbon double bond in a ring structure, wherein the branched substituent contains at least one carbon-carbon double bond.

[0049] In some embodiments, the precursor gas includes limonene and / or limonene derivatives.

[0050] In some embodiments, the limonene derivative includes a monoterpene or other functionalized derivative.

[0051] In some embodiments, the monoterpene derivative is pinene (C) 10 H 16 ), Karen (C 10 H 16 ), Camphen (C 10 H 16 ), terpinene (C 10 H 16 ), phellandrene (C 10 H 16 ), Sabinen (C 10 H 16 ), terpinolene (C 10 H 16 ) includes one or more of the following.

[0052] In some embodiments, the limonene derivatives include limonene oxidation / epoxidation derivatives.

[0053] In some embodiments, the limonene oxidation / epoxidation derivatives include carvone (2-methyl-5-(prop-1-en-2-yl)cyclohexa-2-en-1-one, C 10 H 14 O), carveol (2-methyl-5-(prop-1-en-2-yl)cyclohexa-2-en-1-ol, C 10 H 16 O), limonene-1,2-oxide (1,2-epoxy-p-mentha-8-ene, C 10 H 16 O), limonene dioxide (1,2;8,9-diepoxy-p-menthane, C 10 H 16 O2), perillyl alcohol (4-(prop-1-en-2-yl)cyclohexa-1-ene-1-methanol, C 10 H 16 O), perillic acid (4-(prop-1-en-2-yl)cyclohexa-1-enecarboxylic acid, C 10 H 14 O2), α-terpineol (p-mentha-1-en-8-ol, C 10 H 18 O), limonene hydroperoxide (4-(prop-1-en-2-yl)cyclohexa-1-en-1-yl hydroperoxide, C 10 H 16 O2) of one or more.

[0054] In some embodiments, the limonene derivatives include limonene addition derivatives and limonene hydrogenation derivatives.

[0055] In some embodiments, the limonene addition derivatives and limonene hydrogenation derivatives include dihydrolimonene (4-(propan-2-yl)-1-methylcyclohexa-1-ene, C 10 H 18 ), tetrahydrolimonene (p-menthane, C 10 H 20), dihydrocarbon (2-methyl-5-(propan-2-yl)cyclohexane-1-one, C 10 H 18 O), dihydrocarbeol (2-methyl-5-(propan-2-yl)cyclohexane-1-ol, C 10 H 20 O), Limonene hydrochloride (4-(propan-2-yl)-1-methylcyclohexa-1-yl chloride, C 10 H 17 Cl), limonene hydrobromide (4-(propan-2-yl)-1-methylcyclohexa-1-yl bromide, C 10 H 17 Br), limonene maleic anhydride adduct (2,5-dioxabicyclo[2.2.2]octane-3,6-dione derivative, C 14 H 20 O3), hydrogenated limonene polymer ([C 10 H 16 ] n ) includes one or more of the following.

[0056] In some embodiments, the limonene derivative includes limonene esterified or other functionalized derivatives.

[0057] In some embodiments, the limonene esterification or other functionalized derivative is carbyl acetate (2-methyl-5-(prop-1-en-2-yl)cyclohexa-2-en-1-yl acetate, C 12 H 20 O2), Carbyl propionate (2-methyl-5-(prop-1-en-2-yl)cyclohexa-2-en-1-ylpropanoate, C 13 H 22 O2), dihydrocarbyl acetate (2-methyl-5-(propan-2-yl)cyclohexane-1-yl acetate, C 12 H 22 O2), Limonene Acrylate (4-(prop-1-en-2-yl)-1-methylcyclohexa-1-en-1-yl acrylate, C 13 H 20O2), Limonene methacrylate (4-(propa-1-en-2-yl)-1-methylcyclohexa-1-en-1-yl 2-methylpropa-2-enoate, C 14 H 22 O2), periryl acetate (4-(prop-1-en-2-yl)cyclohexa-1-en-1-yl acetate, C 12 H 18 O2), epoxidized limonene acrylate (1,2-epoxy-4-(propa-1-en-2-yl)-1-methylcyclohexa-1-yl acrylate, ~C 13 H 20 O3), limonene carbonate (4-(propa-1-en-2-yl)-1-methyl-2-oxabicyclo[2.2.2]octan-3-one, C 10 H 16 Contains one or more of the following (O3):

[0058] In some embodiments, the precursor gas is pulsed.

[0059] In some embodiments, the plasma is continuous.

[0060] In some embodiments, the plasma is selected from Ar plasma, He plasma, N2 plasma, or a mixture thereof.

[0061] In some embodiments, the reactive gas is selected from H2, O2, CO2, NH3, and mixtures thereof.

[0062] In some embodiments, the reactive gas is supplied in a continuous manner.

[0063] In some embodiments, the underlying layer formed using method flow 100 contains carbon-carbon double bonds.

[0064] The order of steps in method flow 100 is merely an example, and the order can be changed in other embodiments. For example, in some embodiments, steps 130 and 140 are performed simultaneously. For example, in some embodiments, steps 120, 130, and 140 are performed simultaneously. For example, in some embodiments, step 140 is performed before step 130.

[0065] In some embodiments, the method flow 100 may include other additional steps. For example, in some embodiments, there may be an additional step for supplying a second reactive gas. For example, in some embodiments, there may be an additional step for supplying a second plasma. For example, in some embodiments, there may be an additional step for supplying a second precursor gas. For example, in some embodiments, there may be an additional step for supplying a second purge gas.

[0066] In some embodiments, the additional precursor gas includes an aromatic compound.

[0067] In some embodiments, the additional precursor gas is selected from a list consisting of benzene, alkylbenzene, toluene, ethylbenzene, xylene, julen, aniline, phenol, benzoic acid, biphenyl, mesitylene, styrene, toluidine, toluic acid, cresol, and naphthalene. In some embodiments, the additional precursor gas is selected from a list consisting of o-xylene, m-xylene, and p-xylene. The same applies to toluic acid and cresol.

[0068] In some embodiments, the additional precursor gas includes alkylbenzene. In some embodiments, the alkylbenzene includes trimethylbenzene. In some embodiments, the alkylbenzene includes 1,2,4-trimethylbenzene.

[0069] In some embodiments, the additional precursor gas includes hydrocarbons. In some embodiments, the additional precursor gas includes alkanes. In some embodiments, the additional precursor gas includes linear alkanes. In some embodiments, the additional precursor gas includes branched alkanes. In some embodiments, the additional precursor gas includes one or more of methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, and decane.

[0070] In some embodiments, the additional precursor gas includes an aliphatic hydrocarbon.

[0071] In some embodiments, additional precursor gases are selected from alkylbenzenes such as 1,2,4-trimethylbenzene and organic acid anhydrides such as 2-hydroxy-2-methylpropiophenone.

[0072] In some embodiments, the additional precursor gas comprises a dicarboxylic acid anhydride. In some embodiments, the dicarboxylic acid anhydride comprises a pyromellitic dianhydride. In some embodiments, the additional precursor gas comprises an anhydride such as furan-2,5-dione (maleic anhydride). The anhydride may be a dianhydride, for example, pyromellitic dianhydride (PMDA). In some embodiments, the additional precursor gas may be any other monomer having two reactive groups that react with the reactants.

[0073] In some embodiments, the additional precursor gas is selected from ethylenediaminetetraacetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 4,4'-biphthalic acid anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride.

[0074] In some embodiments, the additional precursor gas includes pyromellitic dianhydride (PMDA).

[0075] In some embodiments, the reactive gas and / or additional reactive gas includes a diamine. In some embodiments, the diamine is selected from the list consisting of 1,6-diaminohexane, 1,4-diaminocyclohexane, and 1,4-diaminobenzene.

[0076] In some embodiments, the diamine is selected from a list consisting of 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,4-bis(aminomethyl)cyclohexane, 2-methyl-1,5-pentanediamine, 2,2-dimethyl-1,3-propanediamine, 1,3-propanediamine, propylenediamine, 2-methyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-pentanediamine, and 1,2-pentanediamine.

[0077] In some embodiments, the reactive gas and / or additional reactive gases include, for example, 1,6-diaminohexane, 1,3-diaminopentane, triamines such as tris(2-aminoethyl)amine, or cyclic compounds containing at least two primary amine groups, such as 1,4-diaminocyclohexane or p-phenylenediamine. In some embodiments, the substrate is in contact with the reactive gas and / or additional reactive gases before contacting the precursor gas. In some embodiments, the substrate is in contact with the precursor gas before contacting the reactive gas and / or additional reactive gases.

[0078] In some embodiments, the plasma employs a plasma gas containing noble gases.

[0079] In some embodiments, the noble gas includes argon.

[0080] In some embodiments, the plasma gas further contains hydrogen.

[0081] In some embodiments, the plasma gas contains, essentially consists of, or comprises a noble gas such as argon. In some embodiments, the plasma gas contains, essentially consists of, or comprises a noble gas and hydrogen. In some embodiments, the plasma gas contains, essentially consists of, or comprises argon and hydrogen.

[0082] In some embodiments, the plasma gas contains Ar, is essentially composed of Ar, or is composed of Ar. In some embodiments, the plasma gas contains He, is essentially composed of He, or is composed of He. In some embodiments, the plasma gas contains Ar and He, is essentially composed of them, or is composed of them. In some embodiments, the plasma gas contains Ar and H2, is essentially composed of them, or is composed of them. In some embodiments, the plasma gas contains Ar and N2, is essentially composed of them, or is composed of them. In some embodiments, the plasma gas contains Ar, H2, and N2, is essentially composed of them, or is composed of them. In some embodiments, the plasma gas contains He and H2, is essentially composed of them, or is composed of them. In some embodiments, the plasma gas contains He, H2, and N2, is essentially composed of them, or is composed of them. In some embodiments, the plasma gas contains Ar, H2, and formic acid, is essentially composed of them, or is composed of them. In some embodiments, the plasma gas contains Ar, N2, and formic acid, is essentially composed of them, or is composed of them.

[0083] In some embodiments, the plasma may be a remote or indirect plasma, and the plasma-generated species to which the substrate is exposed may consist substantially of radicals. Such approaches may be referred to as radical-enhanced atomic layer deposition (RE-ALD). Any plasma gas as disclosed herein may be employed in a remote or indirect plasma configuration. In some embodiments, the plasma gas includes a mixture of argon and H2. When a remote or indirect plasma is employed, the substrate may be separated from the plasma by a mesh, a perforated plate, or similar.

[0084] In some embodiments, the plasma gas includes a noble gas. Additionally or alternatively, the noble gas may include one or more of the following reactants: oxygen reactants, nitrogen reactants, boron reactants, and carbon reactants. Suitable oxygen reactants can be selected from O2, O3, H2O, H2O2, N2O, NO, NO2, and NO3. Suitable nitrogen reactants can be selected from N2, NH3, and N2H2. Suitable carbon reactants may include hydrocarbons such as alkanes like CH4, formic acid, and isopropanol. Suitable boron reactants may include hydrogen boride such as B2H6 and B3H6N3, and suitable sulfur reactants may include hydrogen sulfide (H2S), carbon disulfide (CS2), and sulfur (S). Suitable phosphorus reactants may include phosphine (PH3) and white phosphorus.

[0085] In some embodiments, the plasma gas includes noble gases and hydrogen. For example, the plasma gas may include Ar and H2.

[0086] In some embodiments, the plasma gas comprises a noble gas and a silicon (Si) precursor and / or a carbon (C) precursor. In some embodiments, the precursor comprises Si and C. In some embodiments, the precursor comprises a Si-C bond. In some embodiments, the precursor comprises an alkyl group, alkenyl group, alkynyl group, or allyl group bonded to silicon. In some embodiments, the precursor comprises an alkylamino group bonded to Si. In some embodiments, the alkylamino is selected from -NMe2, -NEt2, -NEtMe, -NHtBu, -N(iPr)2, -N(sBu)2, -N(SiMe3)2, and -N(SiEt3)2. In some embodiments, the precursor comprises an alkoxy group bonded to Si. In some embodiments, the alkoxy group is selected from -OMe, -OEt, -OiPr, -OtBu, -OsBu, -OtPn, -OSiMe3, or -OSiEt3.

[0087] For example, an oxygen plasma may include an O2 plasma, i.e., a plasma employing a plasma gas containing O2. For example, an oxygen plasma may include an H2O plasma, i.e., a plasma gas employing a plasma gas containing H2O, e.g., Ar and H2O, or consisting of them essentially. In some embodiments, the plasma gas contains O2 and Ar. In some embodiments, the plasma gas contains O2 and Ar, or consists of them essentially. Advantageously, it has been found that treating a substrate with an O2 plasma for 2 seconds according to embodiments of this disclosure improves the adhesion of the organometallic resist, and in particular, allows for defect-free printing of feature areas with smaller critical dimensions. While the subject matter of this disclosure is not bound to any particular theory or mode of operation, this may be relevant to substrates having a polar component with increased surface energy. These plasmas are assumed to decrease the H-terminal carbon atoms on the surface and increase the O on the surface. In some embodiments, these specific plasmas employ a plasma output of less than 500 W for a 300 mm wafer and may be maintained for up to 60 seconds, for example, 2 to 5 seconds, to avoid surface damage and modification of deeper layers of the underlying substrate. Other conditions may be modified to adjust plasma stability and the degree of modification to the underlying layer. Although a small sacrifice is sometimes seen for dose reduction due to surface modification, the dose reduction is still high and is considered an acceptable trade-off for improved adhesion.

[0088] In some embodiments, parts of the process may be omitted. For example, in some embodiments, step 120 is omitted. For example, in some embodiments, step 130 is omitted. For example, in some embodiments, step 140 is omitted. For example, in some embodiments, step 160 is omitted.

[0089] Advantageously, the substrate formed using embodiments of the method according to this disclosure exhibits dose reduction. Advantageously, the substrate formed using embodiments of the method according to this disclosure exhibits low edge roughness (LER).

[0090] Figure 2 illustrates a timing sequence 200 suitable for use in a method flow 100 according to some embodiments of the present disclosure. The timing sequence 200 includes a seal gas period 220, a plasma period 230, a reactive gas period 240, a precursor gas period 250, and a purge gas period 260.

[0091] In the embodiment shown in Figure 2, the seal gas is supplied during the seal gas period 220, which begins before the plasma period 230 and continues throughout the entire sequence. The plasma is supplied during the plasma period 230, which begins before the reactive gas period 240. The reactive gas is supplied during the reactive gas period 240, which begins before the precursor gas period 250. The precursor gas is pulsed during the precursor gas period 250, which overlaps with the plasma period 230 and the reactive gas period 240. The purge gas is pulsed during the purge gas period 260 to purge the reaction chamber.

[0092] The composition and behavior of the plasma, reactive gas, precursor gas, and substrate in timing sequence 200 are similar to those of the plasma, reactive gas, precursor gas, and substrate in method flow 100.

[0093] As used herein, pulse duration means the period during which a gas (e.g., precursor, reactant, inert gas, and / or carrier gas) flows into the reaction chamber and / or during which power (e.g., power to generate plasma) is applied. The height and / or width of the illustrated pulse duration do not necessarily indicate the amount or duration of a particular pulse.

[0094] Purge may involve exposing the substrate to an inert gas, such as a noble gas like argon.

[0095] In some embodiments, a precursor gas pulse includes pulses of multiple microprecursor gases. In some embodiments, a reactive gas pulse includes pulses of multiple microreactive gases. The precursor gas and reactive gas may generally be called reactive species, and the corresponding pulses may be called reaction pulses.

[0096] The timing sequence 200 is merely an example, and the duration and start point of each period may vary in other embodiments. For example, in some embodiments, the plasma period 230 and the reactive gas period 240 are started simultaneously. For example, in some embodiments, the seal gas period 220, the plasma period 230, and the reactive gas period 240 are started simultaneously. For example, in some embodiments, the reactive gas period 240 is started before the plasma period 230.

[0097] In some embodiments, other periods are provided. For example, in some embodiments, there are two or more reactive gas periods. For example, in some embodiments, there are two or more plasma periods. For example, in some embodiments, there are two or more precursor gas periods. For example, in some embodiments, there are two or more purge gas periods.

[0098] In some embodiments, parts of the period are omitted. For example, in some embodiments, the seal gas period is omitted. For example, in some embodiments, the plasma period is omitted. For example, in some embodiments, the reactive gas period is omitted. For example, in some embodiments, the purge gas period is omitted.

[0099] Advantageously, the substrate formed using the timing sequence of the method according to this disclosure exhibits dose reduction. Advantageously, the substrate formed using embodiments of the method according to this disclosure exhibits low edge roughness (LER).

[0100] Figure 3 is a schematic diagram of a flow chart 300 of a method for forming a substrate on a substrate according to some embodiments of the present disclosure. Step 310 includes providing the substrate in a reaction chamber. Next, step 320 involves introducing a sealing gas into the reaction chamber. Next, step 330 involves introducing a precursor gas into the reaction chamber. Next, step 335 involves purging the reaction chamber. Next, step 340 involves introducing a reactive gas into the reaction chamber. Next, step 350 involves introducing plasma into the reaction chamber. Next, step 355 involves purging the reaction chamber.

[0101] The method flow 300 also includes subcycles 360 and 370. Subcycle 360 ​​comprises steps 330 and 335, and is repeated one or more times (e.g., several times) until a sufficient amount of precursor gas is adsorbed onto the substrate. Subcycle 370 comprises steps 340, 350, and 355, and is repeated one or more times (e.g., several times) until the gas in the reaction chamber has reacted sufficiently. Subcycles 360 and 370 together form cycle 380, which is repeated one or more times until the desired substrate is formed.

[0102] The composition and behavior of the plasma, reactive gas, precursor gas, and substrate in method flow 300 are similar to those of the plasma, reactive gas, precursor gas, and substrate in method flow 100.

[0103] The sequence of steps in method flow 300 is merely an example, and the sequence can be changed in other embodiments. For example, in some embodiments, steps 340 and 350 are performed simultaneously. For example, in some embodiments, step 350 is performed before step 340.

[0104] In some embodiments, other additional steps may be provided. For example, in some embodiments, there may be an additional step for supplying a second precursor gas. For example, in some embodiments, there may be an additional step for supplying a second reactive gas. For example, in some embodiments, there may be an additional step for supplying a second plasma. For example, in some embodiments, there may be an additional step for supplying a third purge gas.

[0105] In some embodiments, parts of the process are omitted. For example, in some embodiments, step 320 is omitted. For example, in some embodiments, step 130 is omitted. For example, in some embodiments, step 350 is omitted. For example, in some embodiments, step 355 is omitted.

[0106] Advantageously, the substrate formed using embodiments of the method according to this disclosure exhibits dose reduction. Advantageously, the substrate formed using embodiments of the method according to this disclosure exhibits low edge roughness (LER).

[0107] Figure 4 illustrates a timing sequence 400 suitable for use in a flow 300 of a method according to some embodiments of the present disclosure. The timing sequence 400 includes a seal gas period 420, a precursor gas period 430, a first purge gas period 435, a reactive gas period 440, a plasma period 450, and a second purge gas period 455.

[0108] In the embodiment shown in Figure 4, the seal gas is supplied during the seal gas period 420, and the seal gas periods 420 and 220 continue throughout the entire sequence. The amount of precursor gas changes in a pulsed manner during the precursor gas period 430, which begins before the reactive gas period 440. The amount of the first purge gas changes in a pulsed manner during the first purge gas period 435, which begins after the precursor gas period 430. The amount of reactive gas changes in a pulsed manner during the reactive gas period 440, which begins before the plasma period 450. The amount of plasma changes in a pulsed manner during the plasma period 450, which overlaps with the reactive gas period 440. The amount of the second purge gas changes in a pulsed manner during the second purge gas period 455, which begins after the plasma period 450.

[0109] As used herein, pulse duration refers to the period during which a gas (e.g., precursor, reactant, inert gas, and / or carrier gas) flows into the reaction chamber and / or during which power (e.g., power to generate plasma) is applied. The height and / or width of the illustrated pulse duration do not necessarily indicate the amount or duration of a particular pulse.

[0110] The composition and behavior of the plasma, reactive gas, precursor gas, and subsoil in timing sequence 400 are similar to those of the plasma, reactive gas, precursor gas, and subsoil in method flow 100.

[0111] The timing sequence 400 is merely an example, and the duration and start point of each period may vary in other embodiments. For example, in some embodiments, the reactive gas period 440 and the plasma period 450 are started simultaneously. For example, in some embodiments, the plasma period 450 starts before the reactive gas period 440.

[0112] In some embodiments, other periods are provided. For example, in some embodiments, there are two or more precursor gas periods. For example, in some embodiments, there are two or more reactive gas periods. For example, in some embodiments, there are two or more plasma periods. For example, in some embodiments, there is an additional purge gas period.

[0113] In some embodiments, parts of the period are omitted. For example, in some embodiments, the seal gas period is omitted. For example, in some embodiments, the plasma period is omitted. For example, in some embodiments, parts of the purge gas period are omitted.

[0114] Advantageously, the substrate formed using the timing sequence of the method according to this disclosure exhibits dose reduction. Advantageously, the substrate formed using embodiments of the method according to this disclosure exhibits low edge roughness (LER).

[0115] Figure 5 illustrates a semiconductor structure 500 according to some embodiments of the present disclosure. The semiconductor structure 500 includes a substrate 510, a sublayer 520, and a photoresist 530. The sublayer 520 is formed covering the substrate 510, and the photoresist 530 is formed covering the substrate 510. The sublayer 520 contains carbon-carbon double bonds, and the sublayer 520 may be formed using method flow 100 or flow 300. The photoresist 530 may be an organometallic resist or an EUV resist such as a metal oxide resist (MOR). The sublayer 520 of the semiconductor structure 500 is similar to the sublayers of methods flow 100 and flow 300.

[0116] Moving on to Figure 6, a reactor system 600 according to an exemplary embodiment of the present disclosure is illustrated. The reactor system 600 may be used to carry out one or more steps or substeps described herein and / or to form one or more structures or parts thereof described herein.

[0117] The reactor system 600 includes a pair of conductive flat plate electrodes 602 (lower electrode) and 604 (upper electrode) arranged parallel to each other and facing each other inside the reaction chamber 603 (reaction area) 611. Although illustrated with one reaction chamber, the reactor system 600 may include two or more reaction chambers. Plasma can be excited in the reaction chamber 603 by, for example, applying HRF power (e.g., 100 kHz, 13.56 MHz, 27 MHz, 2.45 GHz, or any value in between) to one electrode (e.g., upper electrode 604) from a plasma power supply 630 and electrically grounding the other electrode (e.g., lower electrode 602). A temperature controller can be provided in the lower stage 602 (lower electrode), and the temperature of the substrate 601 placed on it can be maintained at a desired temperature, such as the substrate temperature mentioned above. The upper electrode 604 can function as a gas distribution device such as a shower plate or shower head. The precursor gas, oxygen and / or nitrogen reactant gas, and carrier gas or inert gas (if present), or similar substances may be introduced into the reaction chamber 603 through the shower plate 604 (upper electrode) from the first source 621, the second source 622, the third source 620, and the fourth source 626, respectively, using one or more of the first gas line 623, the second gas line 624, the third gas line 625, and the fourth gas line 627. Although illustrated with four gas lines, the reactor system 600 may include any preferred number of gas lines. For example, the first supply source 621 may correspond to a precursor gas supply source, the second supply source 622 may correspond to a reactive gas supply source (e.g., one or more of a hydrogen reactant supply source, an oxygen reactant supply source, and a nitrogen reactant supply source), the third supply source 620 may correspond to a purge gas supply source, and the fourth supply source 626 may correspond to a metal supply source or a second reactive gas supply source.

[0118] In the reaction chamber 603, a circular duct 613 having an exhaust line 607 can be provided through which gas in the interior 611 of the reaction chamber 603 can be exhausted. In addition, a transfer chamber 605 located below the reaction chamber 603 may be provided with a seal gas line 629 for introducing a seal gas into the interior 611 of the reaction chamber 603 through the interior 616 (transfer zone) of the transfer chamber 605, and a separation plate 614 may be provided to separate the reaction zone and the transfer zone (a gate valve through which the substrate is transferred into or from the transfer chamber 605 is omitted in Figure 6). The transfer chamber may also be provided with an exhaust line 606 connected to an exhaust source 632. In some embodiments, two or more (e.g., all) of the steps of the method flow 100, timing sequence 200, method flow 300, and / or timing sequence 400 may be performed without exposing the substrate to air or other oxygen-containing atmosphere.

[0119] The reactor system 600 may include one or more controllers 628 programmed or otherwise configured to cause one or more method steps to be performed as described herein. As will be understood by those skilled in the art, the controllers 628 are connected to various power sources, heating systems, pumps, robots, and gas flow controllers or reactor valves. For example, a controller 628 may be configured to control the gas flow of precursor gas, reactive gas, and carrier gas into at least one of one or more reaction chambers to form an underlayer or film on the surface of a substrate. The controller may also be configured to perform additional steps as described herein.

[0120] In some embodiments, a dual-chamber reactor (two sections or compartments for processing substrates located close together) can be used, with the reactant gas and noble gas being supplied through a shared line, while the precursor gas is supplied through a separate line.

[0121] Referring to Figure 7, Figure 7 illustrates the characteristics of a substrate formed by a method according to some embodiments of the present disclosure. Figure 7 shows four lines, where Condition 1 (Cond.1), Condition 2 (Cond.2), and Condition 3 (Cond.3) represent the characteristics of a substrate formed by the method of the present disclosure, and Ref. represents the characteristics of a substrate not formed by the method of the present disclosure.

[0122] It can be seen that the doses required for Condition 1 (Cond.1), Condition 2 (Cond.2), and Condition 3 (Cond.3) are less than the dose required for the reference (Ref.). Comparing the doses required for CD=14nm, the reference (Ref.) is approximately 50 mJ / cm². 2 This requires approximately 40 mJ / cm³. Condition 1 (Cond.1) is approximately 40 mJ / cm³. 2 This requires a concentration of approximately 40 mJ / cm³. Condition 2 (Cond.2) is required. 2 It requires less than 40 mJ / cm³, and condition 3 (Cond. 3) is approximately 40 mJ / cm³. 2 It requires a significantly smaller dose than that.

[0123] Referring to Figure 8, Figure 8 illustrates the characteristics of a substrate formed by a method according to some embodiments of the present disclosure. Figure 8 shows four lines, where Condition 1 (Cond.1), Condition 2 (Cond.2), and Condition 3 (Cond.3) represent the characteristics of a substrate formed by the method of the present disclosure, and Ref. represents the characteristics of a substrate not formed by the method of the present disclosure.

[0124] Conditions 1, 2, and 3 show lower LER values ​​than the reference (Ref.) across the dose range, and it can be seen that conditions 1, 2, and 3 show even lower LER variability.

[0125] While embodiments of this disclosure and their advantages have been described in detail, it should be understood that various changes, substitutions, and modifications can be made herein without departing from the spirit and scope of this disclosure as defined by the appended claims. For example, a person skilled in the art will readily understand that many of the features, functions, processes, and materials described herein may vary but remain within the scope of this disclosure. Furthermore, the scope of this application is not intended to be limited to specific embodiments of the processes, machines, manufactures, material compositions, means, methods, and steps described herein. As a person skilled in the art will readily understand from the disclosure, processes, machines, manufactures, material compositions, means, methods, or steps that currently exist or will be developed later and that perform substantially the same functions as or achieve substantially the same results as the corresponding embodiments described herein may be used in accordance with this disclosure. Accordingly, the claims described below are intended to include, within their scope, such processes, machines, manufactures, material compositions, means, methods, or steps. Furthermore, the scope of this disclosure is defined by the appended claims. Furthermore, each claim is constructed as a distinct embodiment, and various combinations of claims and combinations of embodiments are within the scope of this disclosure.

Claims

1. A method for forming a base layer for patterning in lithography, To provide the substrate inside the reaction chamber, Introducing plasma into the reaction chamber, A method comprising introducing a precursor gas into the reaction chamber, wherein the precursor gas contains at least one carbon-carbon double bond.

2. The method according to claim 1, wherein the precursor gas comprises a cyclic hydrocarbon structure having at least one carbon-carbon double bond in its ring structure.

3. The method according to claim 2, wherein the precursor gas further comprises at least one branched substituent on the cyclic hydrocarbon structure.

4. The method according to claim 3, wherein the branched substituent includes at least one carbon-carbon double bond.

5. The method according to claim 1, wherein the precursor gas comprises limonene and / or a limonene derivative.

6. The method according to claim 5, wherein the limonene derivative includes a limonene oxidation derivative / limonene epoxidized derivative.

7. Said limonene oxidation derivative / limonene epoxidation derivative is carvone (2-methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-one, C １０ H １４ O), carveol (2-methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-ol, C １０ H １６ O), limonene-1,2-oxide (1,2-epoxy-p-menth-8-ene, C １０ H １６ O), limonene dioxide (1,2;8,9-diepoxy-p-menthane, C １０ H １６ O ２ ), perillyl alcohol (4-(prop-1-en-2-yl)cyclohex-1-ene-1-methanol, C １０ H １６ O), perillic acid (4-(prop-1-en-2-yl)cyclohex-1-enecarboxylic acid, C １０ H １４ O ２ ), α-terpineol (p-menth-1-en-8-ol, C １０ H １８ O), limonene hydroperoxide (4-(prop-1-en-2-yl)cyclohex-1-en-1-yl hydroperoxide, C １０ H １６ O ２ ). The method according to claim 6, comprising one or more of the above.

8. The method according to claim 5, wherein the limonene derivative includes limonene addition derivatives and limonene hydrogenation derivatives.

9. The limonene addition derivative and limonene hydrogenation derivative are dihydrolimonene (4-(propan-2-yl)-1-methylcyclohexa-1-ene, C １０ H １８ ), tetrahydrolimonene (p-menthane, C １０ H ２０ ), dihydrocarbon (2-methyl-5-(propan-2-yl)cyclohexane-1-one, C １０ H １８ O), dihydrocarbeol (2-methyl-5-(propan-2-yl)cyclohexane-1-ol, C １０ H ２０ O), limonene hydrochloride (4-(propan-2-yl)-1-methylcyclohexa-1-yl chloride, C １０ H １７ Cl), limonene hydrobromide (4-(propan-2-yl)-1-methylcyclohexa-1-yl bromide, C １０ H １７ Br), limonene maleic anhydride adduct (2,5-dioxabicyclo[2.2.2]octane-3,6-dione derivative, C １４ H ２０ O ３ ), hydrogenated limonene polymer ([C １０ H １６ ] ｎ The method according to claim 8, comprising one or more of the following.

10. The method according to claim 5, wherein the limonene derivative includes limonene esterified or other functionalized derivatives.

11. The limonene esterification or other functionalized derivative is carbyl acetate (2-methyl-5-(prop-1-en-2-yl)cyclohexa-2-en-1-yl acetate, C １２ H ２０ O ２ ), carbyl propionate (2-methyl-5-(prop-1-en-2-yl)cyclohexa-2-en-1-ylpropanoate, C １３ H ２２ O ２ ), dihydrocarbyl acetate (2-methyl-5-(propan-2-yl)cyclohexane-1-yl acetate, C １２ H ２２ O ２ ), limonene acrylate (4-(propa-1-en-2-yl)-1-methylcyclohexa-1-en-1-yl acrylate, C １３ H ２０ O ２ ), limonene methacrylate (4-(propa-1-en-2-yl)-1-methylcyclohexa-1-en-1-yl 2-methylpropa-2-enoate, C １４ H ２２ O ２ ), periryl acetate (4-(prop-1-en-2-yl)cyclohexa-1-en-1-yl acetate, C １２ H １８ O ２ ), epoxidized limonene acrylate (1,2-epoxy-4-(propa-1-en-2-yl)-1-methylcyclohexa-1-yl acrylate, ~C １３ H ２０ O ３ ), limonene carbonate (4-(propa-1-en-2-yl)-1-methyl-2-oxabicyclo[2.2.2]octan-3-one, C １０ H １６ O ３ The method according to claim 10, comprising one or more of the following.

12. The method according to claim 1, wherein the underlying layer contains a carbon-carbon double bond.

13. The method according to claim 1, wherein the step of introducing the precursor gas into the reaction chamber is repeated once or more times.

14. The method according to claim 1, wherein the amount of the precursor gas changes in a pulsed manner.

15. The aforementioned plasmas are Ar plasma, He plasma, and N ２ The method according to claim 1, selected from plasma.

16. The method according to claim 1, further comprising introducing a reactive gas into the reaction chamber.

17. The aforementioned reactive gas is H ２ , O ２ CO ２ , and NH ３ The method according to claim 16, wherein the reactive gas is selected from and is continuous.

18. The method according to claim 1, further comprising purging the reaction chamber.

19. The method according to claim 5, wherein the limonene derivative includes a monoterpene or other functionalized derivative.

20. The monoterpene or other functionalized derivative is pinene (C １０ H １６ ), Karen (C １０ H １６ ), Canfen (C １０ H １６ ), terpinene (C １０ H １６ ), phellandrene (C １０ H １６ ), Sabinen (C １０ H １６ ), terpinolene (C １０ H １６ The method according to claim 19, comprising one or more of the following.

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