Semiconductor photoresist composition and method of forming pattern using the same

Abstract

Disclosed are a semiconductor photoresist composition and a method of forming or providing a pattern using the same. The semiconductor photoresist composition may include an organometallic compound represented by Chemical Formula 1 and a solvent. Chemical formula 1

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0039350, filed on March 21, 2024, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] One or more embodiments of the present disclosure relate to a semiconductor photoresist composition and a method of forming or providing a pattern using the semiconductor photoresist composition. Background Art

[0004] Extreme ultraviolet (EUV) lithography has attracted widespread attention as a fundamental technology for manufacturing next-generation semiconductor devices. EUV lithography is a patterning technique that uses EUV radiation with a wavelength of 13.5 nanometers as an exposure light source. EUV lithography enables the formation of fine patterns (e.g., less than or equal to 20 nanometers) during the exposure process in the manufacture of semiconductor devices (e.g., semiconductor chips).

[0005] Extreme ultraviolet (EUV) lithography is enabled by the development of compatible photoresists that can be processed at spatial resolutions of 16 nm or less. Efforts have been or are underway to meet the suboptimal specifications of chemically amplified (CA) photoresists for next-generation devices, such as resolution, speed, and feature roughness (also known as line edge roughness, or LER).

[0006] Intrinsic image blurring caused by acid-catalyzed reactions in polymer-based or type-based photoresists limits resolution of small features, a situation that has long existed in electron-beam (e-beam) lithography. Chemically amplified (CA) photoresists are designed for high sensitivity. However, their elemental composition reduces the photoresist's light absorption at a wavelength of 13.5 nm, potentially reducing their sensitivity. Furthermore, CA photoresists may encounter more difficulties with EUV exposure.

[0007] Chemically amplified (CA) photoresists can struggle with small feature sizes due to roughness issues, and experiments have shown that line edge roughness (LER) of CA photoresists can increase because photospeed can be reduced in part due to the nature of the acid-catalyzed process. Therefore, due to these drawbacks and issues with CA photoresists, the semiconductor industry needs or demands a new type of high-performance photoresist.

[0008] To overcome the shortcomings of chemically amplified (CA) organic photosensitive compositions, inorganic photosensitive compositions have been studied. These compositions are primarily or primarily used for negative-tone patterning and are resistant to removal by a developing composition through chemical modification, a non-chemical amplification mechanism. These compositions contain inorganic elements with higher EUV absorptivity than hydrocarbons. Therefore, they can ensure sensitivity through a non-chemical amplification mechanism and are less susceptible to stochastic effects, resulting in low line-edge roughness and a relatively low number of defects.

[0009] Inorganic photoresists based on tungsten peroxypolyacids mixed with tungsten, niobium, titanium, and / or tantalum have been reported as radiation-sensitive materials for patterning.

[0010] These materials are effective for large-pitch patterning in dual-layer configurations with extreme ultraviolet (EUV), X-ray, and electron beam sources. Improved performance was achieved when using a cationic hafnium metal oxide sulfate (HfSOx) material with a peroxide complexing agent for imaging at 15 nm half-pitch (HP) via projection EUV exposure. The system exhibited high performance for non-CA photoresists and had practical photospeeds approaching those required for EUV photoresists. However, HfSOx materials containing peroxide complexing agents have several practical drawbacks. First, these materials are coated in a corrosive sulfuric acid / hydrogen peroxide mixture, resulting in insufficient shelf life stability. Second, varying the material structure as a composite mixture to improve performance is challenging. Third, development should be performed in a highly concentrated 25 wt% tetramethylammonium hydroxide (TMAH) solution and / or similar solutions.

[0011] To address these issues, research has focused on developing molecules containing tin (Sn) with excellent or moderate extreme ultraviolet light absorption. For organotin polymers in tin-containing molecules, alkyl ligands dissociate through light absorption or generated secondary electrons. The dissociated alkyl ligands then crosslink with adjacent chains through oxo bonds, thereby achieving negative patterning that may not be removed by organic developers. Although such organotin polymers exhibit improved sensitivity and maintain the desired resolution and line edge roughness, the patterning characteristics need further improvement for commercial viability. Summary of the Invention

[0012] One or more aspects of embodiments of the present disclosure are directed to a semiconductor photoresist composition that exhibits excellent or appropriate sensitivity and improved or enhanced stability and coating performance.

[0013] One or more aspects of embodiments of the present disclosure are directed to a method of forming or providing a pattern using the semiconductor photoresist composition.

[0014] Additional aspects will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the presented embodiments of the disclosure.

[0015] The semiconductor photoresist composition according to one or more embodiments may include the organometallic compound represented by Chemical Formula 1 and a solvent.

[0016] Chemical formula 1

[0017]

[0018] In Chemical Formula 1,

[0019] A may be a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclyl group, or a combination thereof,

[0020] L 1 may be a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C2 to C20 alkenylene group,

[0021] X 1 To X 3 Can be independently selected from alkoxy or aryloxy (-OR b , where R b may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof), a carboxyl group (-O(CO)R c , where R c The alkyl group may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof), an alkylamide group, or a dialkylamide group (—NR d R e , where R d and R eeach independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof), an amide group (-NR f (COR g ), where R f and R g and (-NR ), each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof. h C(NR i )R j , where R h 、R i and R j The alkyl groups (-SR 1 ) and (-SR 2 ) may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof), an alkylthio group, or an arylthio group (-SR k , where R k The alkyl radicals may be substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof) and thiocarbonyl (-S(CO)R l , where R l may be selected from hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof, and

[0022] At least since X 1 To X 3 One of the groups selected may be a carboxyl group (-O(CO)R c , where R cThe alkyl radical may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof).

[0023] The method of forming or providing a pattern according to one or more embodiments may include forming or providing an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to form or provide a photoresist layer, patterning the photoresist layer to form or provide a photoresist pattern, and etching the etch target layer using the photoresist pattern as an etch mask.

[0024] The semiconductor photoresist composition according to one or more embodiments may provide a photoresist pattern having improved or enhanced storage stability, coating properties, and / or sensitivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The above and other aspects and features of certain disclosed embodiments will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:

[0026] Figure 1A-1E Each is a cross-sectional view illustrating a method of forming or providing a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0027] Explanation of Figure Numbers

[0028] 100: substrate;

[0029] 102: Film;

[0030] 104: resist bottom layer;

[0031] 106: photoresist layer;

[0032] 106a: unexposed area;

[0033] 106b: exposure area;

[0034] 108: photoresist pattern;

[0035] 110: patterned mask;

[0036] 112: organic layer pattern;

[0037] 114: Thin film pattern. DETAILED DESCRIPTION

[0038] Hereinafter, one or more embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. In the following description of the present disclosure, for the purpose of clarifying the present disclosure, functions or structures that are generally understood by those skilled in the art will not be described.

[0039] In order to clearly illustrate the embodiments of the present disclosure, some descriptions and relationships may be omitted, and substantially the same or similar configuration elements may be represented by the same reference numerals throughout the present disclosure. In addition, since the size and thickness of each configuration shown in the drawings may be arbitrarily displayed for better understanding and ease of description, the embodiments of the present disclosure are not necessarily limited thereto.

[0040] In the accompanying drawings, the thickness of layers, films, panels, regions, and / or the like may be exaggerated for clarity. In the accompanying drawings, the thickness of portions of layers or regions and / or the like may be exaggerated for clarity. It will be understood that if (for example, when) an element, such as a layer, film, region, or substrate, is referred to as being "on" another element, it may be directly on the other element or intervening elements may also be present. If (for example, when) an element is referred to as being "directly on" another element, there may not be intervening elements.

[0041] As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. In addition, the use of "may" when describing embodiments of the present disclosure refers to "one or more embodiments of the present disclosure."

[0042] In the context of the present disclosure, unless defined otherwise, the terms "use," "using," and "used" may be considered synonymous with the terms "utilize," "utilizing," and "utilized," respectively.

[0043] As used herein, the term "about" or similar terms are used as terms of approximation rather than terms of degree, and are intended to take into account the inherent variations in measurements or calculations that one of ordinary skill in the art would recognize. As used herein, "about" or "approximately" is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill 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.

[0044] Any numerical range described herein is intended to include all subranges of the same numerical precision contained within the range. For example, a range of "1.0 to 10.0" is intended to include all subranges between (and including) the minimum value of 1.0 and the maximum value of 10.0, i.e., having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, e.g., 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 specification is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to amend this specification (including the claims) to expressly state any subranges contained within the range explicitly mentioned herein.

[0045] As used herein, "substituted" refers to hydrogen atoms replaced by deuterium, halogen, carboxyl, hydroxyl, thiol, cyano, nitro, -NRR' (wherein, R and R' can each independently be hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein, R, R' and R" can each independently be hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated alicyclic hydrocarbon group, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), The term "unsubstituted" refers to a group consisting of a C1 to C30 alkyl group, a C1 to C30 alkyl group, a C1 to C30 alkyl group, a C1 to C30 alkyl group, a C1 to C30 alkyl group, a C1 to C30 alkyl group, a C1 to C30 alkyl group, a C1 to C30 alkyl group, a C1 to C30 alkyl group, a C1 to C30 alkyl group, a C1 to C20 alkyl group, a C1 to C20 alkyl group, a C1 to C20 alkyl group, a C1 to C20 alkyl group, a C1 to C20 alkyl group, a C1 to C20 alkyl group, a C1 to C20 alkyl group, a C1 to C20 alkyl group, a C1 to C20 alkyl group, or a combination thereof.

[0046] As used herein, if (for example, when) no definition is provided otherwise, "alkyl" refers to a straight-chain or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0047] The alkyl group may be a C1 to C10 alkyl group. For example, the alkyl group may be a C1 to C8 alkyl group, a C1 to C7 alkyl group, a C1 to C6 alkyl group, or a C1 to C5 alkyl group. For example, the C1 to C5 alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a 2,2-dimethylpropyl group.

[0048] As used herein, if (eg, when) no definition is provided otherwise, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0049] The cycloalkyl group may be a C3 to C10 cycloalkyl group, for example, a C3 to C8 cycloalkyl group, a C3 to C7 cycloalkyl group, or a C3 to C6 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but the embodiments of the present disclosure are not limited thereto.

[0050] As used herein, "aryl" refers to a cyclic substituent in which all atoms have p orbitals and these p orbitals are conjugated, and can include monocyclic functional groups, polycyclic functional groups, or fused ring (eg, rings that share adjacent pairs of carbon atoms) functional groups.

[0051] As used herein, unless otherwise defined, "alkenyl" refers to an unsaturated alkenyl group containing at least one double bond as a straight-chain or branched aliphatic hydrocarbon group.

[0052] As used herein, unless otherwise defined, "alkynyl" refers to an unsaturated alkynyl group containing at least one triple bond as a straight or branched aliphatic hydrocarbon group.

[0053] In the chemical formulae described herein, t-Bu refers to tert-butyl.

[0054] As used herein, "heterocyclic group" includes not only aromatic rings, such as "heteroaryl", but also non-aromatic rings, and unless otherwise specified, it refers to a ring containing 2 to 60 carbon atoms, each ring containing one or more heteroatoms, but the embodiments of the present disclosure are not limited thereto. Unless otherwise specified, "heteroatom" refers to an element other than carbon (C), such as nitrogen (N), oxygen (O), sulfur (S), phosphorus (P) or silicon (Si), and may include heteroatom groups, such as SO2, P=O and / or the like, replacing the carbon forming the ring. As used herein, heterocyclic groups include monocyclic rings, ring aggregates, one or more fused ring systems, spirocyclic compounds and / or the like, which contain heteroatoms.

[0055] Semiconductor photoresist compositions according to one or more embodiments are described below.

[0056] The semiconductor photoresist composition according to one or more embodiments may include the organometallic compound represented by Chemical Formula 1 and a solvent.

[0057] Chemical formula 1

[0058]

[0059] In Chemical Formula 1,

[0060] A may be a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclyl group, or a combination thereof,

[0061] L 1may be a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C2 to C20 alkenylene group,

[0062] X 1 To X 3 Can be independently selected from alkoxy or aryloxy (-OR b , where R b may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof), a carboxyl group (-O(CO)R c , where R c The alkyl group may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof), an alkylamide group or a dialkylamide group (—NR d R e , where R d and R e and (-NR ) are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof. f (COR g ), where R f and R g and (-NR ) may each independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof), an amidino group (-NR h C(NR i )R j , where R h 、R i and R jand (-SR 100, -SR 100) each independently represent hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof), an alkylthio group, or an arylthio group (-SR 100). k , where R k The alkyl radicals may be substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof, and thiocarbonyl (-S(CO)R l , where R l may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof, and

[0063] X 1 To X 3 At least one of them can be a carboxyl group (-O(CO)R c , where R c The alkyl radical may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof).

[0064] If (for example, when) an organometallic compound having a cyclic substituent is used as described in the present disclosure, the thermal stability of the film may be high and crystal formation may be suppressed during coating, thereby improving and enhancing coating properties.

[0065] As an example, X 1 To X 3 Can be independently selected from alkoxy or aryloxy (-OR b , where R bmay be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof), a carboxyl group (-O(CO)R c , where R c The alkyl group may be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof), an alkylamide group or a dialkylamide group (-NR d R e , where R d and R e and (-NR ) are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof. f (COR g ), where R f and R g may each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof), an amidino group (-NR h C(NR i )R j , where R h 、R i and R j and (-SR 10, -SR 10) may each independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof), an alkylthio group, or an arylthio group (-SR k , where R kmay be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof), and a thiocarbonyl group (-S(CO)R l , where R l may be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof, and

[0066] Selected from X 1 To X 3 At least one of them may be a carboxyl group (-O(CO)R c , where R c The alkyl radical may be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof).

[0067] For example, X 1 To X 3 Each of the c , where R c The alkyl radical may be hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof).

[0068] In one or more embodiments, R bmay be substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof, and

[0069] R c 、R d 、R e 、R f 、R g 、R h 、R i 、R j 、R k and R l Each of the radicals may independently be hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof.

[0070] In one or more embodiments, from A and L 1 At least one selected from among may include an unsaturated bond.

[0071] If (for example, when) the organometallic compound includes such an unsaturated bond, it can be imparted with solubility in an organic solvent (for example, become soluble in an organic solvent). Therefore, the organometallic compound according to one or more embodiments has relatively excellent or appropriate solubility and storage stability in an organic solvent, and a pattern can be easily or appropriately formed even using a low-concentration developer.

[0072] In one or more embodiments, since it is possible to reduce the bond dissociation energy between the central metal atom and carbon to extreme ultraviolet rays, the semiconductor photoresist composition including the organometallic compound as described in one or more embodiments can exhibit excellent or appropriate sensitivity, and if (for example, when) used to form or provide a pattern, a pattern that does not collapse can be formed or provided even with a high aspect ratio.

[0073] For example, A may include an unsaturated bond, and, for example, A may be a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

[0074] For example, A may be a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C3 to C10 cycloalkenyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heterocyclyl group.

[0075] As an example, A may be a substituted or unsubstituted C6 to C30 aryl group, L 1 It may be a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C2 to C20 alkenylene group.

[0076] If (for example, when) A is a substituted or unsubstituted C6 to C30 aryl group, and L 1 In the case of a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C2 to C20 alkenylene group, the bond dissociation energy of the carbon atom bonded to the central metal atom to extreme ultraviolet rays may be reduced, thereby achieving excellent or appropriate sensitivity.

[0077] For example, A can be substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted indenyl, substituted or unsubstituted tetrahydronaphthyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted cyclooctyl, substituted or unsubstituted cyclononyl, substituted or unsubstituted cyclopentenyl, substituted or unsubstituted cyclohexen ... substituted or unsubstituted cycloheptenyl, substituted or unsubstituted bicyclo[2,2,1]heptyl, substituted or unsubstituted bicyclo[2,2,1]heptenyl, substituted or unsubstituted bicyclo[2,2,1]octyl, substituted or unsubstituted bicyclo[2,2,4]octyl, substituted or unsubstituted tricyclo[3,3,1,1]decyl, substituted or unsubstituted bicyclo[4,3,0]nonyl, substituted or unsubstituted bicyclo[4,4,0]octyl, substituted or unsubstituted pyrrolidinyl group), a substituted or unsubstituted oxoranyl group, a substituted or unsubstituted thioranyl group, a substituted or unsubstituted pyrrole group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted piperidinyl group, a substituted or unsubstituted oxanyl group, a substituted or unsubstituted thianyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyranyl group, or a substituted or unsubstituted thiophyranyl group.

[0078] The organometallic compound can be selected from the compounds listed in Group 1.

[0079] Group 1

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086] The organometallic compound according to one or more embodiments may strongly absorb extreme ultraviolet light at 13.5 nm and may have excellent or appropriate sensitivity to high-energy light.

[0087] In the semiconductor photoresist composition according to one or more embodiments, the content of the organometallic compound may be from about 0.5 wt % to about 30 wt %, for example, from about 1 wt % to about 30 wt %, from about 1 wt % to about 25 wt %, for example, from about 1 wt % to about 20 wt %, for example, from about 1 wt % to about 15 wt %, for example, from about 1 wt % to about 10 wt %, or for example, from about 1 wt % to about 5 wt %, based on 100 wt % of the semiconductor photoresist composition, and the embodiments of the present disclosure are not limited thereto. If (for example, when) the content of the organometallic compound is within the above range, the storage stability and / or etching resistance of the semiconductor photoresist composition may be improved or enhanced, and the resolution characteristics may be improved or enhanced.

[0088] Since the semiconductor photoresist composition according to one or more embodiments may include the organometallic compound as described in one or more embodiments, a semiconductor photoresist composition having excellent or appropriate sensitivity and / or pattern forming performance may be provided.

[0089] The solvent of the semiconductor photoresist composition according to one or more embodiments may be an organic solvent, for example, an aromatic compound (e.g., xylene, toluene and / or the like), an alcohol (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol and / or the like), an ether (e.g., anisole, tetrahydrofuran and / or the like), an ester (n-butyrate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate and / or the like), a ketone (e.g., methyl ethyl ketone, 2-heptanone and / or the like), or a mixture thereof, but the embodiments of the present disclosure are not limited thereto.

[0090] In one or more embodiments, the semiconductor photoresist composition may further include a resin in addition to the organometallic compound and the solvent.

[0091] The resin may be a phenolic resin, which may include at least one aromatic group selected from the groups listed in Group 2.

[0092] Group 2

[0093]

[0094] The resin may have a weight average molecular weight (M) of about 500 g / mol to about 20,000 g / mol. w ).

[0095] The resin may be included in an amount of about 0.1 wt % to about 50 wt % based on the total amount of the semiconductor photoresist composition.

[0096] If (eg, when) the resin is included in the above-mentioned content (eg, amount) range, it may have excellent or appropriate etching resistance and / or heat resistance.

[0097] In one or more embodiments, the semiconductor photoresist composition according to one or more embodiments may be composed of or include the organometallic compound, solvent, and resin described in one or more embodiments. However, the semiconductor photoresist composition according to one or more embodiments may further include additives as needed or desired. Examples of additives may include surfactants, cross-linking agents, leveling agents, organic acids, quenchers, or combinations thereof.

[0098] The surfactant may include, for example, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, or a combination thereof, but embodiments of the present disclosure are not limited thereto.

[0099] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic crosslinking agent, an epoxy-based crosslinking agent, or a polymer-based crosslinking agent, but embodiments of the present disclosure are not limited thereto. It may be a crosslinking agent having at least two substituents that form a crosslink, for example, a compound such as methoxymethylated biuret, butoxymethylated biuret, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanidine, butoxymethylated benzoguanidine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, methyl acrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylolpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and / or the like.

[0100] Leveling agents may be used to improve or enhance the flatness of the coating during the printing process and may be commercially available or commonly available leveling agents.

[0101] The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalene disulfonic acid, methanesulfonic acid, sulfonium fluoride, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, or a combination thereof, but the embodiments of the present disclosure are not limited thereto.

[0102] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, or a combination thereof.

[0103] The amount of additives used can be controlled according to the desired properties.

[0104] In one or more embodiments, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve or enhance the close contact force with the substrate (for example, to improve or enhance the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent can be, for example, a silane compound containing a carbon-carbon unsaturated bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-phenylyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; trimethoxy[3-(phenylamino)propyl]silane and / or the like, but the embodiments of the present disclosure are not limited thereto.

[0105] The semiconductor photoresist composition can form or provide a pattern with a high aspect ratio and no collapse. Therefore, in order to form or provide a fine pattern with, for example, about 5 nanometers to about 100 nanometers, for example, about 5 nanometers to about 80 nanometers, for example, about 5 nanometers to about 70 nanometers, for example, about 5 nanometers to about 50 nanometers, for example, about 5 nanometers to about 40 nanometers, for example, about 5 nanometers to about 30 nanometers, for example, about 5 nanometers to about 20 nanometers, or for example, about 5 nanometers to about 10 nanometers width (for example, line width), the semiconductor photoresist composition can be used for a photolithography process using a wavelength range of about 5 nanometers to about 150 nanometers, (for example, about 5 nanometers to about 100 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers). In one or more embodiments, the semiconductor photoresist composition according to one or more embodiments can be used to realize extreme ultraviolet lithography using an EUV light source with a wavelength of about 13.5 nanometers.

[0106] According to one or more embodiments, a method for forming or providing a pattern using the semiconductor photoresist composition described in one or more embodiments may be provided. For example, the pattern may be a photoresist pattern.

[0107] The method of forming or providing a pattern according to one or more embodiments may include forming or providing an etch target layer on a substrate, coating a semiconductor photoresist composition on the etch target layer to form or provide a photoresist layer, patterning the photoresist layer to form or provide a photoresist pattern, and etching the etch target layer using the photoresist pattern as an etch mask.

[0108] The following reference Figure 1A-1E Methods of forming or providing patterns using semiconductor photoresist compositions are described. Figure 1A-1E Each of them is a cross-sectional view for explaining a method of forming or providing a pattern using a semiconductor photoresist composition according to one or more embodiments.

[0109] Reference Figure 1A , an etching target (e.g., an etching target layer or etching target layer) may be prepared. The etching target may be a thin film 102 that may be formed or provided on the semiconductor substrate 100. Hereinafter, the etching target may be defined as the thin film 102. The surface of the thin film 102 may be cleaned to remove impurities and / or the like remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0110] Subsequently, a resist base layer composition for providing the resist base layer 104 may be spin-coated on the surface of the cleaned thin film 102. However, the embodiments of the present disclosure are not limited thereto, and one or more suitable coating methods, such as spray coating, dip coating, doctor blade coating, printing methods (such as inkjet printing and screen printing), and / or the like, may be used.

[0111] The coating process of the resist base layer may not be provided, and the following description includes the process of coating the resist base layer.

[0112] The applied composition may then be dried and baked to form or provide a resist bottom layer 104 on the thin film 102. The baking (eg, heat treatment) may be performed at about 100°C to about 500°C (eg, about 100°C to about 300°C).

[0113] The resist bottom layer 104 may be located between the substrate 100 and the photoresist layer 106, thereby preventing or reducing non-uniformity (e.g., substantial non-uniformity) in the photoresist line width and patterning capability that may result if (e.g., when) light reflected from the interface between the substrate 100 and the photoresist layer 106 or the hard mask between the layers is scattered onto unintended photoresist areas.

[0114] Reference Figure 1B The photoresist layer 106 may be formed or provided by coating a semiconductor photoresist composition on the resist bottom layer 104. The photoresist layer 106 may be obtained or provided by coating a semiconductor photoresist composition according to one or more embodiments on the thin film 102 on the substrate 100 and then curing it through heat treatment.

[0115] For example, forming a pattern using a semiconductor photoresist composition may include coating the semiconductor photoresist composition on the substrate 100 having the thin film 102 by spin coating, slit coating, inkjet printing, and / or the like, and then drying it to form or provide the photoresist layer 106 .

[0116] The semiconductor photoresist composition has been described in detail and will not be described again here.

[0117] Subsequently, the substrate 100 having the photoresist layer 106 may be subjected to a first baking process (eg, heat treatment). The first baking process may be performed at a temperature of about 80°C to about 120°C.

[0118] Reference Figure 1C , the photoresist layer 106 may be selectively exposed using a patterned mask 110 .

[0119] For example, exposure can use activating radiation of light or beams having a high-energy wavelength (such as EUV (extreme ultraviolet; wavelength of about 13.5 nanometers), electron beam (E-Beam) and / or the like) and light having a short wavelength (such as i-line (wavelength of about 365 nanometers), KrF excimer laser (wavelength of about 248 nanometers), ArF excimer laser (wavelength of about 193 nanometers) and / or the like).

[0120] For example, the light or beam used for exposure according to one or more embodiments may have a wavelength in the range of about 5 nm to about 150 nm and high energy wavelengths, such as EUV (extreme ultraviolet; wavelength 13.5 nm), electron beam (E-Beam) and / or the like.

[0121] The exposed region 106 b of the photoresist layer 106 may have a different solubility from the unexposed region 106 a of the photoresist layer 106 by forming a polymer through a cross-linking reaction (eg, condensation between organometallic compounds) or providing a polymer (eg, condensation between organometallic compounds).

[0122] Subsequently, the substrate 100 may be subjected to a second baking process (eg, heat treatment). The second baking process may be performed at a temperature of about 90° C. to about 200° C. Due to the second baking process, the exposed region 106 b of the photoresist layer 106 may become easily insoluble in a developing solution.

[0123] exist Figure 1D In the embodiment of the present invention, the unexposed regions 106a of the photoresist layer can be dissolved and removed using a developer to form or provide a photoresist pattern 108. For example, the unexposed regions 106a of the photoresist layer can be dissolved and removed using an organic solvent (e.g., 2-heptanone and / or the like) to complete the photoresist pattern 108 corresponding to the negative tone image.

[0124] According to one or more embodiments, the developer used in the method for forming or providing a pattern according to one or more embodiments may be an organic solvent. The organic solvent used in the method for forming or providing a pattern according to one or more embodiments may be, for example, a ketone such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and / or the like; an alcohol such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, and / or the like; an ester such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and / or the like; an aromatic compound such as benzene, xylene, toluene, and / or the like, or a combination thereof.

[0125] However, the photoresist pattern according to one or more embodiments is not necessarily limited to a negative image, but can be formed or provided as a positive image. Here, the developer for forming or providing the positive image can be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or a combination thereof.

[0126] According to one or more embodiments, exposure to light or a beam having a high-energy wavelength (e.g., EUV (extreme ultraviolet; wavelength 13.5 nm), an electron beam (E-Beam), and / or the like) and light having a short wavelength (e.g., i-line (wavelength of approximately 365 nm), a KrF excimer laser (wavelength of approximately 248 nm), an ArF excimer laser (wavelength of approximately 193 nm), and / or the like) may provide the photoresist pattern 108 having a width of approximately 5 nm to approximately 100 nm in thickness. For example, the photoresist pattern 108 may have a width of approximately 5 nm to approximately 90 nm, approximately 5 nm to approximately 80 nm, approximately 5 nm to approximately 70 nm, approximately 5 nm to approximately 60 nm, approximately 5 nm to approximately 50 nm, approximately 5 nm to approximately 40 nm, approximately 5 nm to approximately 30 nm, approximately 5 nm to approximately 20 nm, or approximately 5 nm to approximately 10 nm in thickness.

[0127] In one or more embodiments, the photoresist pattern 108 may have a half pitch of less than or equal to about 50 nanometers (e.g., less than or equal to about 40 nanometers, such as less than or equal to about 30 nanometers, such as less than or equal to about 20 nanometers, or such as less than or equal to about 10 nanometers), and a line width roughness of less than or equal to about 5 nanometers, less than or equal to about 3 nanometers, less than or equal to about 2 nanometers, or less than or equal to about 1 nanometer.

[0128] Subsequently, the photoresist pattern 108 can be used as an etching mask to etch the resist bottom layer 104. Through this etching process, an organic layer pattern 112 can be formed or provided. The organic layer pattern 112 can also have a width (eg, line width) corresponding to the photoresist pattern 108.

[0129] Reference Figure 1EBy using the photoresist pattern 108 as an etching mask, the exposed thin film 102 can be etched. As a result, the thin film can be formed or provided as a thin film pattern 114.

[0130] The etching of the thin film 102 may be, for example, dry etching using an etching gas, and the etching gas may be, for example, CHF 3 , CF 4 , Cl 2 , BCl 3 , and a mixture thereof.

[0131] During the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process performed using the EUV light source may have a width (e.g., line width) corresponding to the photoresist pattern 108. For example, the thin film pattern 114 may have a width (e.g., line width) of about 5 nanometers to about 100 nanometers, which may be equal to the width of the photoresist pattern 108. For example, the thin film pattern 114 formed or provided using the photoresist pattern 108 formed or provided by the exposure process performed using the EUV light source may have a width (e.g., line 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, and, for example, a width (e.g., line width) less than or equal to about 20 nanometers, which is similar or similar to the width of the photoresist pattern 108.

[0132] Hereinafter, the present disclosure will be described in more detail by way of examples of preparing the semiconductor photoresist composition described in one or more embodiments. However, the present disclosure is not technically limited to the following examples.

[0133] Synthesis of organometallic compounds

[0134] Synthesis Example 1

[0135] 30 g of tetrakisdiethylamino tin was added to a 250 ml Schlenk flask, and then 74 ml of anhydrous n-hexane was added, and the mixture was stirred at -20°C under a nitrogen atmosphere.

[0136] Subsequently, 40.5 ml of a 2.0 M cyclopentylmagnesium bromide diethyl ether solution was slowly added at -20°C for 1 hour, and then the temperature was raised to room temperature, followed by stirring at room temperature for 6 hours. The resulting reaction solution was filtered under an anhydrous nitrogen atmosphere to remove the solids produced therein, and the filtrate was concentrated under reduced pressure to obtain Compound M-1 shown below.

[0137]

[0138] Subsequently, 50 g of the compound shown in M-1 was added to a 500 ml Schlenk flask, and 124 ml of anhydrous toluene was added at -10 °C under a nitrogen atmosphere.

[0139] Here, 23 g of anhydrous acetic acid was slowly added at -10°C, and then the temperature was raised to room temperature, and the resulting reaction solution was stirred for 1 hour. The obtained reaction solution was concentrated under reduced pressure to finally obtain the compound shown as P-1.

[0140]

[0141] Synthesis Example 2

[0142] 30 g of tetrakis(diethylamino)tin was added to a 250 ml Schlenk flask, and then 74 ml of anhydrous n-hexane was added, and the mixture was stirred at -20°C under a nitrogen atmosphere.

[0143] Here, 40.5 ml of a 2.0 M cyclohexylmagnesium bromide diethyl ether solution was slowly added at -20°C for 1 hour, then the temperature was raised to room temperature, and the resulting reaction solution was stirred at room temperature for 6 hours. The resulting reaction solution was filtered under an anhydrous nitrogen atmosphere, and the mixture was filtered to remove the solid produced therein. The filtrate was then concentrated under reduced pressure to obtain the compound shown as M-2.

[0144] Subsequently, 50 g of the compound shown as M-2 was added to a 500 ml Schlenk flask, and 120 ml of anhydrous toluene was added at -10°C under a nitrogen atmosphere.

[0145] Then, 27.4 g of anhydrous propionic acid was slowly added at -10°C, and after the temperature was raised to room temperature, the resulting reaction solution was stirred at room temperature for 1 hour. The resulting reaction solution was concentrated under reduced pressure to finally obtain the compound shown in P-2.

[0146]

[0147] Synthesis Example 3

[0148] A compound shown as P-3 was obtained in substantially the same manner as in Synthesis Example 2, except that cyclopentanemethyl magnesium bromidediethyl ether was used instead of cyclohexyl magnesium bromide diethyl ether.

[0149]

[0150] Synthesis Example 4

[0151] A compound shown as P-4 was obtained in substantially the same manner as in Synthesis Example 2, except that benzylmagnesium bromide diethyl ether was used instead of cyclohexylmagnesium bromide diethyl ether.

[0152]

[0153] Synthesis Example 5

[0154] A compound shown as P-5 was obtained in substantially the same manner as in Synthesis Example 1, except that 3-methylbenzylmagnesium bromidediethyl ether was used instead of cyclohexylmagnesium bromide diethyl ether.

[0155]

[0156] Synthesis Example 6

[0157] The compound shown in P-6 was obtained in substantially the same manner as in Synthesis Example 1, except that 1-bicyclo[2.2.2]octylmagnesium bromide tetrahydrofuran was used instead of cyclohexylmagnesium bromide diethyl ether.

[0158]

[0159] Synthesis Example 7

[0160] A compound shown as P-7 was obtained in substantially the same manner as in Synthesis Example 2, except that exo-2-norbonyl magnesium bromidediethyl ether was used instead of cyclohexylmagnesium bromide diethyl ether.

[0161]

[0162] Synthesis Example 8

[0163] A compound shown as P-8 was obtained in substantially the same manner as in Synthesis Example 1, except that 1-adamantylmagnesium bromidetetrahydrofuran was used instead of cyclohexylmagnesium bromide diethyl ether.

[0164]

[0165] Synthesis Example 9

[0166] A compound shown as P-9 was obtained in substantially the same manner as in Synthesis Example 1, except that 3-cyclohexenyl magnesium bromidediethyl ether was used instead of cyclohexyl magnesium bromide diethyl ether.

[0167]

[0168] Synthesis Example 10

[0169] A compound shown as P-10 was obtained in substantially the same manner as in Synthesis Example 1, except that 3-thiophenemethylmagnesium bromidediethyl ether was used instead of cyclohexylmagnesium bromide diethyl ether.

[0170]

[0171] Comparative Synthesis Example 1

[0172] A compound shown as P-11 was obtained in substantially the same manner as in Synthesis Example 1, except that normal butylmagnesium bromide diethylether was used instead of cyclohexylmagnesium bromide diethylether.

[0173]

[0174] Comparative Synthesis Example 2

[0175] The compound shown in P-12 was obtained in substantially the same manner as in Synthesis Example 1, except that n-butylmagnesium bromide diethyl ether was used instead of cyclohexylmagnesium bromide diethyl ether and anhydrous ethanol was used instead of acetic acid.

[0176]

[0177] Preparation of semiconductor photoresist compositions

[0178] Examples 1 to 10 and Comparative Examples 1 and 2

[0179] Each compound in Synthesis Examples 1 to 10 and Comparative Synthesis Examples 1 and 2 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a concentration of 3 wt %, and then filtered through a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare a photoresist composition.

[0180] Evaluation 1: Sensitivity evaluation

[0181] A linear array of 50 circular pads with a diameter of 500 μm was projected using extreme ultraviolet light (Lawrence Berkeley National Laboratory Micro Exposure Tool (MET)) onto a wafer coated with each of the photoresist compositions of Examples 1 to 10 and Comparative Examples 1 and 2. Here, the exposure time of the pads was adjusted to apply an increasing dose of extreme ultraviolet light to each pad.

[0182] Subsequently, the resist and substrate were exposed on a hot plate at 160°C for 120 seconds and then baked. The resulting baked films were each immersed in a developer (2-heptanone) for 30 seconds and then washed with the same developer (2-heptanone) for another 10 seconds to form or provide a negative image, i.e., to remove the unexposed portions of the coating. Finally, the process was completed by baking on a hot plate at 150°C for 2 minutes.

[0183] Ellipsometers were used to measure the residual resist thickness of the exposed pads. The residual resist thickness was measured for each exposure dose and then plotted as a function of exposure dose to evaluate the Dg (energy level at which development is completed) of different resist types or classes based on the following criteria. The results are shown in Table 1.

[0184] Evaluation criteria (Dg value)

[0185] A: less than 16mJ / cm 2

[0186] B: greater than or equal to 16mJ / cm 2 and less than 23mJ / cm 2

[0187] C: greater than or equal to 23mJ / cm 2 And less than 30mJ / cm 2

[0188] D: greater than or equal to 30mJ / cm 2

[0189] Evaluation 2: Storage stability evaluation

[0190] The organometallic compounds according to Examples 1 to 10 and Comparative Examples 1 and 2 were evaluated for storage stability according to the following criteria. The results are shown in Table 1.

[0191] Storage stability

[0192] Each semiconductor photoresist composition according to Examples 1 to 10 and Comparative Example 1 was allowed to stand at room temperature (20±5° C.) for a specific time, and then the degree of precipitation was visually inspected and evaluated according to the following storage standards.

[0193] Evaluation Criteria

[0194] -○: Can be stored for more than 2 months

[0195] -△: Can be stored for more than 2 weeks but less than 2 months.

[0196] -X: Storage time is less than 2 weeks

[0197] Table 1

[0198]

[0199] Referring to the results in Table 1, the semiconductor photoresist composition of the Example exhibited excellent sensitivity and significantly improved storage stability compared to the semiconductor photoresist composition of the Comparative Example.

[0200] Hereinafter, certain embodiments of the present disclosure have been described and illustrated. However, it should be apparent to those skilled in the art that the present disclosure is not limited to the described embodiments and that appropriate modifications and conversions may be made without departing from the spirit and scope of the present disclosure. Therefore, such modified or converted embodiments may not be understood separately from the technical ideas and aspects of one or more embodiments of the present disclosure, and the modified embodiments may be within the scope of the appended claims of the present disclosure and their equivalents.

Claims

1. A semiconductor photoresist composition comprising: an organometallic compound represented by Chemical Formula 1; as well as Solvent: Chemical formula 1 Wherein, in Chemical Formula 1, A is a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclyl group, or a combination thereof, L 1 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C2 to C20 alkenylene group, X 1 To X 3 Each independently selected from -OR b Represents an alkoxy or aryloxy group, wherein R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, or a combination thereof; and -O(CO)R c Represents a carboxyl group, where R c is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; -NR d R e An alkylamide or dialkylamide group, wherein R d and R e are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; -NR f (COR g ) represents an amide group, wherein R f and R g are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; -NR h C(NR i )R j represents an amidine group, wherein R h 、R i and R j are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; -SR k represents an alkylthio or arylthio group, wherein R k is a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl, a substituted or unsubstituted C2 to C20 alkynyl, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof; and is represented by -S(CO)R l represents a thiocarbonyl group, wherein R l is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof, and At least one selected from X 1 To X 3 is composed of -O(CO)R c Represents a carboxyl group, where R c is hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 aralkyl, or a combination thereof.

2. The semiconductor photoresist composition according to claim 1, wherein: X 1 To X 3 Each independently selected from -OR b Represents an alkoxy or aryloxy group, wherein R b is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof; and -O(CO)R c Represents a carboxyl group, where R c is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; d R e An alkylamide or dialkylamide group, wherein R d and R e are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; -NR f (COR g ) represents an amide group, wherein R f and R g are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; -NR h C(NR i )R j represents an amidine group, wherein R h 、R i and R j are each independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof; -SR k represents an alkylthio or arylthio group, wherein R k is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C2 to C10 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C20 aralkyl group, or a combination thereof; and is represented by -S(CO)R l represents a thiocarbonyl group, wherein R l is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof, and Selected from X 1 To X 3 At least one of them is composed of -O(CO)R c Represents a carboxyl group, where R c is hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C7 to C20 aralkyl, or a combination thereof.

3. The semiconductor photoresist composition according to claim 1, wherein: R b is substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof, and R c 、R d 、R e 、R f 、R g 、R h 、R i 、R j 、R k and R l each is independently hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted isopropyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted 2,2-dimethylpropyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted vinyl, substituted or unsubstituted propenyl, substituted or unsubstituted butenyl, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted xylyl, substituted or unsubstituted benzyl, or a combination thereof.

4. The semiconductor photoresist composition according to claim 1, wherein: From A and L 1 At least one selected from includes an unsaturated bond.

5. The semiconductor photoresist composition according to claim 1, wherein: A is a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C3 to C10 cycloalkenyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heterocyclyl group, or a combination thereof.

6. The semiconductor photoresist composition according to claim 1, wherein: A is a substituted or unsubstituted C6 to C30 aryl group, and L 1 is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C2 to C20 alkenylene group.

7. The semiconductor photoresist composition according to claim 1, wherein: A is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted indenyl, substituted or unsubstituted tetrahydronaphthyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted cyclooctyl, substituted or unsubstituted cyclononyl, substituted or unsubstituted cyclopentenyl, substituted or unsubstituted cyclohexenyl, substituted or unsubstituted cycloheptenyl, substituted or unsubstituted bicyclo[2,2,1]heptyl, substituted or unsubstituted bicyclo[2,2,1]heptenyl, substituted or unsubstituted bicyclo[2,2,1]oct ... substituted or unsubstituted bicyclo[2,2,4]octyl, substituted or unsubstituted tricyclo[3,3,1,1]decyl, substituted or unsubstituted bicyclo[4,3,0]nonyl, substituted or unsubstituted bicyclo[4,4,0]octyl, substituted or unsubstituted pyrrolidinyl, substituted or unsubstituted oxolanyl, substituted or unsubstituted thiopyranyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophenyl, substituted or unsubstituted piperidinyl, substituted or unsubstituted oxahexyl, substituted or unsubstituted thioheterocyclohexyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyranyl or substituted or unsubstituted thiopyranyl.

8. The semiconductor photoresist composition according to claim 1, wherein: The organometallic compound is one selected from the compounds listed in Group 1: Group 1 9. The semiconductor photoresist composition according to claim 1, wherein: The content of the organic metal compound is 0.5 wt % to 30 wt % based on 100 wt % of the semiconductor photoresist composition.

10. The semiconductor photoresist composition according to claim 1, wherein The semiconductor photoresist composition further includes an additive of a surfactant, a cross-linking agent, a leveler, an organic acid, a quencher, or a combination thereof.

11. A method for forming a pattern, comprising: providing an etching target layer on a substrate; applying the semiconductor photoresist composition according to claim 1 on the etching target layer to provide a photoresist layer; patterning the photoresist layer to provide a photoresist pattern; as well as The etch target layer is etched using the photoresist pattern as an etch mask.

12. The method according to claim 11, wherein: The photoresist pattern is provided using light having a wavelength of 5 nm to 150 nm.

13. The method according to claim 11, wherein: The photoresist pattern has a width of 5 nanometers to 100 nanometers.

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