Semiconductor photoresist composition and method of forming pattern using the same

Abstract

A semiconductor photoresist composition includes: an organometallic compound represented by Chemical Formula 1; and a solvent, chemical formula 1 # imgabs0 #, and a method of forming a pattern includes: forming an etching target layer on a substrate; coating an etching target layer with the semiconductor photoresist composition according to the claim 1 to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; and etching the etching target layer using the photoresist pattern as an etching mask.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0110007 filed in the Korean Intellectual Property Office on August 22, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] One or more aspects of the 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 is considered an important (even necessary) technology for manufacturing next-generation semiconductor devices. EUV lithography is a pattern forming technology that uses EUV rays with a wavelength of 13.5 nanometers (nm) as an exposure source. When EUV lithography is applied, very fine patterns (e.g., less than or equal to 20 nm) can be formed in the exposure process during the manufacture of semiconductor devices.

[0005] Extreme ultraviolet (EUV) lithography is accomplished (e.g., performed by developing a compatible photoresist) where the development (e.g., the process of developing the photoresist) can be performed with a spatial resolution of less than or equal to 16 nm. Currently, efforts are being made to overcome or mitigate the inadequate or unsuitable specifications of chemically amplified (CA) photoresists for next generation devices, such as resolution, photospeed, and / or feature roughness (also referred to as line edge roughness or LER).

[0006] Intrinsic image blurring due to acid-catalyzed reactions in polymer-based types or species of photoresists may limit resolution of small feature sizes, a phenomenon known to occur in electron beam (e-beam) lithography. Chemically amplified (CA) photoresists are designed to achieve relatively high sensitivity, but may have some additional difficulties with EUV exposure because their elemental makeup can reduce the absorbance of the photoresist at 13.5 nm and therefore reduce its sensitivity.

[0007] In addition, CA photoresists may have difficulty with small feature sizes due to roughness issues, and experiments often show that the line edge roughness (LER) of CA photoresists increases as photospeed decreases, at least in part due to the nature (e.g., properties) of the acid catalyst process. Therefore, a new relatively high performance photoresist is needed or desired in the semiconductor industry to help overcome these deficiencies and problems of CA photoresists.

[0008] In order to overcome the above-mentioned disadvantages of chemically amplified (CA) organic photosensitive compositions, an inorganic photosensitive composition has been developed. The inorganic photosensitive composition is mainly used for negative patterning, which resists removal by a developer composition due to chemical modification by a non-chemical amplification mechanism. The inorganic composition contains an inorganic element having a higher EUV absorption rate than hydrocarbons, and thus can ensure sensitivity (e.g., sensitivity to EUV light) by a non-chemical amplification mechanism, and furthermore can be less sensitive to stochastic effects, and thus can have relatively low line edge roughness and a relatively small number of defects.

[0009] Inorganic photoresists based on peroxypolyacids of tungsten mixed with tungsten, niobium, titanium and / or tantalum have been reported as radiation-sensitive materials for patterning. (See also US 5061599 as an example; and H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986; the entire contents of each of the two examples are incorporated herein by reference.) These materials can be used or adapted to pattern large pitches of bilayer configurations as effectively as extreme ultraviolet (deep UV), X-ray and / or electron beam sources.

[0010] Recently, improved performance has been obtained when cationic hafnium metal oxide sulfate (HfSOx) materials are used with peroxy complexing agents for imaging 15 nm half-pitch (HP) by projection EUV exposure (e.g., when cationic hafnium metal oxide sulfate (HfSOx) materials are used with peroxy complexing agents for imaging 15 nm half-pitch (HP) by projection EUV exposure) (see also US2011-0045406 as an example; and J.K. Stowers, A.T. Lecky, M. . Kocsis, BL Clark, DA Keszler, A. Grenville, CN Anderson, PP Naulleau (JK Stowers, A. Telecky, M. Kocsis, BL Clark, DA Keszler, A. Grenville, CN Anderson, PP Naulleau, Proc. SPIE, 7969, 796915, 2011; the entire contents of each of the two examples are incorporated herein by reference). This system exhibits relatively high performance for non-CA photoresists and has a feasible photosensitivity close to that required (or needed) for EUV photoresists. However, hafnium metal oxide sulfate materials with peroxy complexing agents have some practical disadvantages. First, these materials are coated in the form of a mixture of corrosive sulfuric acid / hydrogen peroxide and have insufficient or unsuitable shelf life stability. Second, as a composite mixture, structural changes to it to achieve performance improvements are not easily achieved. Third, development should be performed in a very high concentration of 25 wt % tetramethylammonium hydroxide (TMAH) solution and / or similar solutions.

[0011] Recently, research has been conducted to explore tin-containing molecules because they can have excellent or suitable absorption of extreme ultraviolet rays. Among organotin polymer compounds, alkyl ligands can be dissociated by light absorption and / or secondary electrons generated thereby, and can be cross-linked with adjacent chains through oxygen bonds, thereby enabling negative patterning that can not be removed by organic developers. Such organotin polymers can show greatly improved sensitivity while maintaining suitable resolution and line edge roughness, but their patterning characteristics need to be further improved 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 exhibiting improved contrast performance.

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

[0014] A semiconductor photoresist composition according to one or more embodiments includes an organometallic compound represented by Chemical Formula 1 and a solvent.

[0015] Chemical formula 1

[0016]

[0017] In Chemical Formula 1,

[0018] M can be selected from tetravalent metals, pentavalent metals and hexavalent metals,

[0019] R 1 It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, L a -OR a (Where L a is a single bond, or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), or C(O)-R b (where R b is hydrogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C30 aryl),

[0020] R 2 to R 4 and C(O)-R are each independently hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, c (where R c may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), P(O)OR d R e (where R d and R e may be each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), P(O)OR f OR g (where R f and R gmay be each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), S(O)R h (where R h may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), or S(O)2R i (where R i may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group),

[0021] R 2 to R 4 At least one of them may be a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a C(O)-R c (where R c may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C30 aryl), P(O)OR d R e (where R d and R e may be each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), P(O)OR f OR g (where R f and R g may be each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), S(O)R h (where R h may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), or S(O)2R i (where R i may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group); and / or R 2 to R 4 Adjacent groups therein are connected to each other to form a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group,

[0022] X can be halogen, OL b -C(O)-R j (Where L b may be a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C2 to C20 alkenylene group, and R jThe amino group may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or a substituted or unsubstituted C6 to C30 aryl group, or any suitable combination thereof), an alkylamino group, and / or a dialkylamino group (e.g., —NR k R l , where R k and R l The alkyl groups may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or (e.g., any suitable) combination thereof), an amide group (e.g., —NR m (COR n ), where R m and R n The alkyl radicals may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or (e.g., any suitable) combination thereof), or an amidino group (e.g., —NR o C(NR p )R q , where R o , R p and R q may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or (e.g., any suitable) combination thereof),

[0023] n1 and m1 may each independently be an integer from 1 to 5,

[0024] p is an integer from 0 to 4, and

[0025] 4≤n1+m1+p≤6.

[0026] According to one or more embodiments, the method of forming (or providing) a pattern includes: forming (or providing) an etching target layer on a substrate; coating the semiconductor photoresist composition on the etching target layer to form (or provide) a photoresist layer; patterning the photoresist layer to form (or provide) a photoresist pattern; and etching the etching target layer using the photoresist pattern as an etching mask.

[0027] The semiconductor photoresist composition according to one or more embodiments may provide a photoresist pattern having improved contrast properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] These and / or other aspects will become apparent and more easily understood by reading the following description of the embodiments in conjunction with the accompanying drawings, in which:

[0029] Figures 1 to 5 Each 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.

[0030] [Explanation of Reference Numerals]

[0031] 100: Substrate

[0032] 102: Film

[0033] 104: Resist base

[0034] 106: Photoresist layer

[0035] 106a: Unexposed area

[0036] 106b: Exposure area

[0037] 108: Photoresist pattern

[0038] 110: Patterned mask

[0039] 112: Organic layer pattern

[0040] 114: Thin film pattern DETAILED DESCRIPTION

[0041] In the following, embodiments of the present disclosure are described in more detail with reference to the accompanying drawings. In the following description of the present disclosure, for the sake of clarity of the present disclosure, functions or structures well known to those skilled in the art will not be described in detail.

[0042] In order to clearly illustrate the present disclosure, some descriptions and relationships are not provided, and the same or similar configuration elements are represented by the same reference numerals throughout the disclosure. In addition, since the size and thickness of each configuration shown in the drawings are arbitrarily shown for better understanding and ease of description, the present disclosure is not necessarily limited thereto.

[0043] In the accompanying drawings, the thickness of each layer, film, panel, region and / or the like is magnified and / or exaggerated for clarity. It should be understood that if an element (such as a layer, film, region or substrate) is referred to as being "on" another element (for example, when an element (such as a layer, film, region or substrate) is referred to as being "on" another element), the element may be directly on the other element (for example, without any intermediate elements therebetween), or intermediate elements may also be present.

[0044] It should be understood that although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish between various elements. Therefore, without departing from the teachings of the present invention, the first element may be referred to as the second element. Similarly, the second element may be referred to as the first element.

[0045] 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.

[0046] It will also be understood that the terms “includes / including” and / or “comprises / comprising”, when used in the present specification, specify the presence of stated features, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, elements, components and / or groups thereof.

[0047] As used herein, the terms "use," "using," and "used" may be considered synonymous with the terms "utilize," "utilizing," and "utilized," respectively.

[0048] As used herein, expressions such as "at least one of," "one of," and "selected from," when preceding a series of elements, modify the entire series of elements rather than the individual elements in the series. For example, "at least one selected from a, b, and c," "at least one of a, b, or c," and "at least one of a, b, and / or c" may indicate including only a, only b, only c, including (e.g., simultaneously) both a and b, including (e.g., simultaneously) both a and c, including (e.g., simultaneously) both b and c, including all of a, b, and c, or variations thereof.

[0049] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0050] In addition, the use of “may” when describing embodiments of the present disclosure refers to “one or more embodiments of the present disclosure.”

[0051] For ease of description, spatially relative terms such as "beneath," "below," "lower," "above," "upper," "bottom," "top," and the like may be used herein to describe the relationship of one element or feature shown in the figures to another (other) element or feature. It should be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation shown in the figures. For example, if the device in the figure is turned over, the elements described as being "below" or "beneath" other elements or features will now be oriented "above" or "on" the other elements or features. Thus, the term "below" may include both above and below orientations. The device may be oriented in other ways (rotated 90 degrees or other orientations), and the spatially relative descriptors used herein should be interpreted accordingly.

[0052] As used herein, the terms "substantially," "about," and similar terms are used as terms of approximation rather than degree, and are intended to account for the inherent deviations in measured or calculated values ​​that one of ordinary skill in the art would recognize. "About" or "approximately" as used herein include the stated value and mean 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 the errors associated with the measurement of the particular quantity (i.e., the limitations of the measurement system). For example, "about" may mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.

[0053] Any numerical range described herein is intended to include all sub-ranges of the same numerical precision that fall within the range. For example, the range of "1.0 to 10.0" is intended to include all sub-ranges between (and including) the minimum value 1.0 and the maximum value 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, such as (for example) 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits that fall within it, and any minimum numerical limit described in this specification is intended to include all higher numerical limits that fall within it. Therefore, the applicant reserves the right to amend this specification (including the claims) to explicitly state any sub-ranges that fall within the range explicitly stated herein.

[0054] The term "substituted" as used herein refers to a hydrogen atom replaced by deuterium, halogen, hydroxyl, thiol, cyano, nitro, carbonyl, -NRR' (wherein R and R' can each independently be hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein R, R' and R " may each independently be hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 alkylsilanyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a C1 to C20 thioether group, and / or (e.g., any suitable) combination thereof. "Unsubstituted" means that a hydrogen atom is not replaced by another substituent and remains as a hydrogen atom.

[0055] If no definition is provided otherwise (eg, when no definition is provided otherwise), the "alkyl" described herein refers to a straight chain or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" without any double bond or triple bond.

[0056] 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, without limitation. For example, the C1 to C5 alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and / or a 2,2-dimethylpropyl group.

[0057] If a definition is not otherwise provided (eg, when a definition is not otherwise provided), "cycloalkyl" as described herein refers to a monovalent cyclic aliphatic hydrocarbon group.

[0058] The cycloalkyl group may be a C3 to C10 cycloalkyl group, such as 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, and / or a cyclohexyl group, but the present disclosure is not limited thereto.

[0059] The "aryl group" described herein refers to a substituent in which all atoms in a cyclic substituent have p orbitals and these p orbitals are conjugated, and may include a monocyclic or condensed-ring polycyclic (ie, rings sharing adjacent pairs of carbon atoms) functional groups.

[0060] Unless otherwise defined, the "alkenyl group" described herein refers to an aliphatic unsaturated alkenyl group including at least one double bond in a straight or branched aliphatic hydrocarbon group.

[0061] Unless otherwise defined, "alkynyl" described herein refers to an aliphatic unsaturated alkynyl group including at least one triple bond in a straight or branched aliphatic hydrocarbon group.

[0062] In the chemical formulas set forth herein, t-Bu refers to tert-butyl.

[0063] Hereinafter, semiconductor photoresist compositions according to one or more embodiments are described.

[0064] The semiconductor photoresist composition according to one or more embodiments includes the organometallic compound represented by Chemical Formula 1 and a solvent.

[0065] Chemical formula 1

[0066]

[0067] In Chemical Formula 1,

[0068] M may be one (eg, any one) of a tetravalent metal, a pentavalent metal, or a hexavalent metal,

[0069] R 1 It may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, L a -OR a (Where L a is a single bond, or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), or C(O)-R b (where R b is hydrogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C30 aryl),

[0070] R 2 to R 4 and C(O)-R are each independently hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, c (where R cmay be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), P(O)OR d R e (where R d and R e may be each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), P(O)OR f OR g (where R f and R g may be each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), S(O)R h (where R h may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), or S(O)2R i (where R i may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group),

[0071] R 2 to R 4 At least one of them may be a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a C(O)-R c (where R c may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C30 aryl), P(O)OR d R e (where R d and R e may be each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), P(O)OR f OR g (where R f and R g may be each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), S(O)R h (where R h may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), or S(O)2R i (where R i may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group); and / or R 2 to R4 Adjacent groups therein may be connected to each other to form (or provide) a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group,

[0072] X can be halogen, OL b -C(O)-R j (Where L b may be a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C2 to C20 alkenylene group, and R j The amino group may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or a substituted or unsubstituted C6 to C30 aryl group, or any suitable combination thereof, an alkylamino group, or a dialkylamino group (e.g., —NR k R l , where R k and R l The alkyl groups may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or (e.g., any suitable) combination thereof), an amide group (e.g., —NR m (COR n ), where R m and R n The alkyl radicals may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or (e.g., any suitable) combination thereof), or an amidino group (e.g., —NR o C(NR p )R q , where R o , R p and R q may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or (e.g., any suitable) combination thereof),

[0073] n1 and m1 may each independently be an integer from 1 to 5,

[0074] p can be an integer from 0 to 4, and

[0075] 4≤n1+m1+p≤6.

[0076] The organometallic compound of the present disclosure improves sensitivity by introducing functional groups that can appropriately stabilize free radical compounds generated during exposure, and maximizes or increases the solubility difference between exposed and unexposed areas of the photoresist layer in the developer, thereby improving pattern formability and process margin.

[0077] The functional group capable of suitably stabilizing the free radical compound may be located at the same position as R in Chemical Formula 1. 2 to R 4 and may be a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a C(O)-R c (where R c may be hydrogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C30 aryl), P(O)OR d R e (where R d and R e may be each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), P(O)OR f OR g (where R f and R g may be each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), S(O)R h (where R h may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group), or S(O)2R i (where R i may be a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group); and / or R 2 to R 4 Adjacent groups therein may be connected to each other to form (or provide) a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group.

[0078] For example, if R 2 to R 4 At least one of the cIf a carbonyl group is present, the following reaction mechanism may occur as shown in Reaction Scheme 1, and the free radical generated after exposure may be stabilized by the carbonyl group and become more sensitive to the photosensitive reaction. Therefore, the difference in physical properties between the exposed area and the unexposed area is maximized or increased, thereby achieving excellent or suitable contrast performance.

[0079] Reaction Scheme 1

[0080]

[0081] For example, M can be selected from Sn, Sb, I, Te, In, Ag, Ni, Bi, and Po.

[0082] In some embodiments, M may be Sn.

[0083] The organotin compound according to the present disclosure may also include a hydrolyzable group and a photosensitive reactive group together (eg, simultaneously), in addition to the functional group capable of stabilizing the free radical compound in the central metal tin.

[0084] For example, R 2 to R 4 At least one of them may be a substituted or unsubstituted C2 to C10 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, a C(O)-R c (where R c may be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl), P(O)OR d R e (where R d and R e may be each independently a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group), P(O)OR f OR g (where R f and R g may be each independently a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group), S(O)R h (where R h and R g may be each independently a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group), or S(O)2R i (where R i may be a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group); or

[0085] Through R 2 to R4 A substituted or unsubstituted C3 to C20 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C20 aromatic hydrocarbon group formed by connecting adjacent groups therein.

[0086] For example, R 2 to R 4 At least one of them may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted xylyl group, C(O)-R c (where R c may 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl), C(R r )=C(R s )(R t )(where R r , R s and R t may each 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl), P(O)OR d R e (where R d and R e may each independently be a 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl), P(O)OR f OR g (where R f and R gmay each independently be a 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl), S(O)R h (where R h may 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl), or S(O)2R i (where R i may 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl); and / or

[0087] R 2 to R 4 Adjacent groups therein may be connected to each other to form a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted cycloheptyl group, a substituted or unsubstituted cyclooctyl group, a substituted or unsubstituted cyclononyl group, or a substituted or unsubstituted cyclodecyl group.

[0088] For example, R 2 to R 4 At least one of can be selected from the substituents listed in Group 1-1; and / or

[0089] R 2 to R 4 Adjacent groups therein may be connected to each other to form one of the ring groups listed in Groups 1-2.

[0090] Group 1-1

[0091]

[0092] Group 1-2

[0093]

[0094] In Group 1-1 and Group 1-2, * is the same as R 2 to R 4 The corresponding carbon to which one or more are attached.

[0095] For example, R 1 It may 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, or L a -OR a (Where L a may be a substituted or unsubstituted C1 to C10 alkylene group, and R a may be a substituted or unsubstituted C1 to C10 alkyl group).

[0096] In some embodiments, R 1 It may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, a substituted or unsubstituted tert-pentyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted vinyl group, 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, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, and / or (e.g., any suitable) combination thereof, and

[0097] R a The group may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2,2-dimethylpropyl group, and / or (e.g., any suitable) combination thereof.

[0098] For example, X can be halogen, OL b -C(O)-R j (Where L bmay be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C2 to C10 alkenylene group, R j The amino group may 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, or any suitable combination thereof, an alkylamino group, or a dialkylamino group (e.g., —NR k R l , where R k and R l The alkyl radicals 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, or (e.g., any suitable) combination thereof), an amide group (e.g., -NR m (COR n ), where R m and R n The alkyl radicals 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, or (e.g., any suitable) combination thereof), or an amidino group (e.g., -NR o C(NR p )R q , where R o , R p and R q The radicals 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, or (e.g., any suitable) combination thereof).

[0099] For example, X can be halogen or OL b -C(O)-R j (Where L b may be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C2 to C10 alkenylene group, and R jThe group may 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, or (e.g., any suitable) combination thereof.

[0100] In one or more embodiments, X may be OL b -C(O)-R j (Where L b may be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C2 to C10 alkenylene group, and R j The group may 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, or (e.g., any suitable) combination thereof.

[0101] For example, R j may 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 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, and / or (e.g., any suitable) combination thereof, and

[0102] The organometallic compound may be selected from the compounds listed in Group 2.

[0103] Group 2

[0104]

[0105] The organometallic compound may have excellent or suitable sensitivity due to its relatively high reactivity to extreme ultraviolet light of about 13.5 nm and / or to additional secondary electrons generated thereby.

[0106] The organometallic compound may be included in an amount of about 1 wt % to about 30 wt %, such as about 1 wt % to about 25 wt %, such as about 1 wt % to about 20 wt %, such as about 1 wt % to about 15 wt %, such as about 1 wt % to about 10 wt %, or such as about 1 wt % to about 5 wt %, based on 100 wt % of the semiconductor photoresist composition, and the present disclosure is not limited thereto. When the content (e.g., amount) of the organometallic compound is within any of the above ranges, the storage stability and etching resistance of the semiconductor photoresist composition are improved, and the resolution characteristics are improved.

[0107] Since the semiconductor photoresist composition according to one or more embodiments includes the organometallic compound, a semiconductor photoresist composition having excellent or appropriate sensitivity and stability may be provided.

[0108] The solvent of the semiconductor photoresist composition according to one or more embodiments may be an organic solvent and may be, for example, selected from the following: aromatic compounds (e.g., xylene, toluene and / or similar compounds), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol and / or similar alcohols), ethers (e.g., anisole, tetrahydrofuran and / or similar ethers), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate and / or similar esters), ketones (e.g., methyl ethyl ketone, 2-heptanone and / or similar ketones) and / or (e.g., any suitable) mixtures thereof, but the present disclosure is not limited thereto.

[0109] The semiconductor photoresist composition according to one or more embodiments may further include a resin in addition to the organometallic compound and the solvent of the embodiments of the present disclosure.

[0110] The resin may be a phenolic resin comprising at least one aromatic moiety of Group 3.

[0111] Group 3

[0112]

[0113] The resin may have a weight average molecular weight of about 500 to about 20,000.

[0114] The resin may be included in an amount of about 0.1 wt % to about 50 wt % based on the total amount (100 wt %) of the semiconductor photoresist composition.

[0115] If the resin is included in the above content (eg, amount) range (eg, when the resin is included in the above content (eg, amount) range), the semiconductor photoresist composition may have excellent or appropriate etching resistance and heat resistance.

[0116] The semiconductor photoresist composition according to one or more embodiments may include an organometallic compound, a solvent and a resin according to an embodiment of the present disclosure (e.g., composed of an organometallic compound, a solvent and a resin according to an embodiment of the present disclosure). However, the semiconductor photoresist composition according to one or more embodiments may also include suitable additives as needed. Examples of additives may be surfactants, cross-linking agents, leveling agents, organic acids, quenchers and / or (e.g., any suitable) combinations thereof.

[0117] The surfactant may include, for example, alkylbenzene sulfonates, alkyl pyridinium salts, polyethylene glycol, quaternary ammonium salts, and / or (eg, any suitable) combinations thereof, but the present disclosure is not limited thereto.

[0118] The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, an acrylic crosslinking agent, an epoxy resin-based crosslinking agent, and / or a polymer-based crosslinking agent, but the present disclosure is not limited thereto. The crosslinking agent may have at least two substituents that form crosslinks, such as compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, polyurethane acrylate, acryl methacrylate, 1,4-butanediol diglycidyl ether, glycidol, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, trimethylpropane triglycidyl ether, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, and / or methoxymethylated thiourea and / or similar compounds.

[0119] The leveling agent may be used to improve coating smoothness during printing, and may be any suitable (eg, commercially available) leveling agent.

[0120] The organic acid may include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalene disulfonic acid, methanesulfonic acid, fluorinated sulfonium salts, malonic acid, citric acid, propionic acid, methacrylic acid, oxalic acid, lactic acid, glycolic acid, succinic acid, and / or (e.g., any suitable) combinations thereof, but the present disclosure is not limited thereto.

[0121] The quencher can be diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, and / or (eg, any suitable) combinations thereof.

[0122] The amount of the additive can be controlled or selected depending on the desired or suitable properties.

[0123] In one or more embodiments, the semiconductor photoresist composition may further include a silane coupling agent as an adhesion enhancer to improve the close contact force with the substrate (e.g., to improve the adhesion of the semiconductor photoresist composition to the substrate). The silane coupling agent may be, for example: a silane compound including a carbon-carbon unsaturated bond, such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, vinyl tri(β-methoxyethoxy)silane; 3-methacryloxypropyl trimethoxysilane; 3-acryloxypropyl trimethoxysilane; p-phenylyl trimethoxysilane; 3-methacryloxypropyl methyl dimethoxysilane; 3-methacryloxypropyl methyl diethoxysilane; trimethoxy [3- (phenylamino) propyl] silane and / or similar silane compounds, but the present disclosure is not limited thereto.

[0124] Semiconductor photoresist composition can be formed into a pattern with a relatively high aspect ratio without collapse. Therefore, in order to form (or provide) a fine pattern with a width of, for example, about 5nm to about 100nm, for example, about 5nm to about 80nm, for example, about 5nm to about 70nm, for example, about 5nm to about 50nm, for example, about 5nm to about 40nm, for example, about 5nm to about 30nm or about 5nm to about 20nm, the semiconductor photoresist composition can be used for a photoresist process using a wavelength of about 5nm to about 150nm, for example, about 5nm to about 100nm, about 5nm to about 80nm, about 5nm to about 50nm, about 5nm to about 30nm, for example, about 5nm to about 20nm, or about 5nm to about 10nm. Therefore, 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 13.5nm.

[0125] According to one or more embodiments, a method for forming (or providing) a pattern using a semiconductor photoresist composition according to an embodiment of the present disclosure is provided. For example, the pattern produced may be a photoresist pattern.

[0126] According to one or more embodiments, the method of forming (or providing) a pattern includes: forming (or providing) an etching target layer on a substrate; coating the semiconductor photoresist composition on the etching target layer to form (or provide) a photoresist layer; patterning the photoresist layer to form (or provide) a photoresist pattern; and etching the etching target layer using the photoresist pattern as an etching mask.

[0127] In the following, reference is made to Figures 1 to 5 A method for forming (or providing) a pattern using the semiconductor photoresist composition is described. Figures 1 to 5is 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.

[0128] Reference Figure 1 , prepare an object for etching. The object for etching may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the object for etching is limited to the thin film 102. The entire (e.g., the entire or substantially the entire) surface of the thin film 102 is cleaned to remove impurities and / or the like remaining on the surface. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0129] Subsequently, a resist base layer composition for providing a resist base layer 104 is spin-coated on the surface of the cleaned thin film 102. However, one or more embodiments are not limited thereto, and one or more suitable coating methods, such as spray coating, dip coating, blade coating, printing methods (e.g., inkjet printing and screen printing), and / or the like, may be used.

[0130] Hereinafter, a process including coating of a resist bottom layer is described. However, in some embodiments, a coating process of a resist bottom layer may not be provided (eg, may be omitted).

[0131] Then, the applied composition is dried and baked to form (or provide) a resist bottom layer 104 on the thin film 102. The baking may be performed at about 100°C to about 500°C, for example, about 100°C to about 300°C.

[0132] The resist bottom layer 104 is formed between the substrate 100 and the photoresist layer 106, and therefore, if radiation reflected from the interface between the substrate 100 and the photoresist layer 106 and / or the hard mask between the layers is scattered into an unintended (or unexpected) photoresist area (for example, when the radiation is scattered into an unintended (or unexpected) photoresist area), non-uniformity in pattern formability and non-uniformity in photoresist line width can be prevented or reduced.

[0133] Reference Figure 2 The photoresist layer 106 is formed by coating the semiconductor photoresist composition of the embodiment of the present disclosure on the resist bottom layer 104. The photoresist layer 106 can be obtained by coating the semiconductor photoresist composition on the thin film 102 formed on the substrate 100 and then curing it by heat treatment.

[0134] For example, forming a pattern using a semiconductor photoresist composition may include coating a semiconductor resist composition on the substrate 100 coated with the thin film 102. The semiconductor photoresist composition may be coated by spin coating, slit coating, inkjet printing, and / or the like, and then may be dried to form (or provide) a photoresist layer 106.

[0135] The semiconductor photoresist composition has been described herein and will not be described again in detail.

[0136] Subsequently, a first baking process is performed on the substrate 100 having the photoresist layer 106. The first baking process may be performed at about 80°C to about 120°C.

[0137] Reference Figure 3 , the patterned mask 110 may be used to selectively expose the photoresist layer 106 .

[0138] For example, exposure can use activating radiation using the following light: light with a high-energy wavelength, such as extreme ultraviolet (EUV; wavelength of about 13.5nm), electron beam (E-Beam), etc.; as well as i-line (wavelength of about 365nm), KrF excimer laser (wavelength of about 248nm), ArF excimer laser (wavelength of about 193nm), etc.

[0139] For example, light 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 a relatively high energy wavelength, such as extreme ultraviolet (EUV; wavelength 13.5 nm), electron beam (E-Beam), etc.

[0140] The exposed region 106 b of the photoresist layer 106 has a different solubility from the unexposed region 106 a of the photoresist layer 106 , wherein the exposed region 106 b forms a polymer through a cross-linking reaction (eg, condensation between organic metal compounds).

[0141] Subsequently, a second baking process is performed on the substrate 100. The second baking process may be performed at a temperature of about 90° C. to about 200° C. As a result of the second baking process, the exposed region 106 b of the photoresist layer 106 becomes substantially insoluble in the developer.

[0142] exist Figure 4 In the process, the unexposed area 106a of the photoresist layer is dissolved and removed by a developer to form a photoresist pattern 108. For example, an organic solvent such as 2-heptanone and / or the like is used to dissolve and remove the unexposed area 106a of the photoresist layer to complete the photoresist pattern 108 corresponding to the negative image.

[0143] As described above, the developer (e.g., developer composition) 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, selected from: ketones (e.g., methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and / or similar ketones), alcohols (e.g., 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, and / or similar alcohols), esters (e.g., propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and / or similar esters), aromatic compounds (e.g., benzene, xylene, toluene, and / or similar aromatic compounds) and / or (e.g., any suitable) combinations thereof.

[0144] However, the photoresist pattern according to one or more embodiments is not necessarily limited to a negative image, but may also be formed to have a positive image. Herein, the developer used to form (or provide) a positive image may be a quaternary ammonium hydroxide composition, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and / or (e.g., any suitable) combination thereof.

[0145] As described above, exposure to light having relatively high energy such as extreme ultraviolet (EUV; wavelength of 13.5 nm), electron beam (E-Beam), and light having a certain wavelength such as i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), ArF excimer laser (wavelength of about 193 nm), etc. can provide a photoresist pattern 108 having a width of about 5 nm to about 100 nm. For example, the photoresist pattern 108 may have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, about 5 nm to about 20 nm, or about 5 nm to about 10 nm.

[0146] In some embodiments, the photoresist pattern 108 may have a half pitch less than or equal to about 50 nm, for example, less than or equal to about 40 nm, for example, less than or equal to about 30 nm, for example, less than or equal to about 20 nm, for example, less than or equal to about 10 nm, and the photoresist pattern 108 may have a line width roughness less than or equal to about 5 nm, less than or equal to about 3 nm, less than or equal to about 2 nm, or less than or equal to about 1 nm.

[0147] Subsequently, the resist bottom layer 104 is etched using the photoresist pattern 108 as an etching mask. Through this etching process, an organic layer pattern 112 is formed. The organic layer pattern 112 may also have a width corresponding to the width of the photoresist pattern 108.

[0148] Reference Figure 5The exposed thin film 102 is etched by using the photoresist pattern 108 as an etching mask. Thus, the thin film is formed into a thin film pattern 114.

[0149] 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 / or a mixed gas thereof.

[0150] In the exposure process, the thin film pattern 114 formed using the photoresist pattern 108 may have a width corresponding to the width of the photoresist pattern 108, wherein the photoresist pattern 108 is formed by the exposure process performed using the EUV light source. For example, the thin film pattern 114 may have a width of 5 nm to 100 nm, which is equal to the width of the photoresist pattern 108. For example, like the width of the photoresist pattern 108 (which is formed by the exposure process performed using the EUV light source), the thin film pattern 114 formed using the photoresist pattern 108 may have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm, and more specifically may have a width less than or equal to about 20 nm.

[0151] Hereinafter, the present disclosure will be described in more detail by way of an example of the preparation of a semiconductor photoresist composition according to an embodiment of the present disclosure. However, the present disclosure is not technically limited by the following examples.

[0152] Synthesis of organometallic compounds

[0153] Synthesis Example 1: Synthesis of the compound represented by Chemical Formula 2

[0154] In 250mL 2-necked round-bottom flasks, Ph SnCl (20 grams, 51.9mmol) was dissolved in 100mL anhydrous tetrahydrofuran (THF), and then cooled to 0°C in an ice bath, and slowly added a THF solution (62.3mmol) of 2-butanone-3-magnesium bromide thereto. When the addition was complete, the mixture was stirred for 12 hours at room temperature (25°C). After distillation under reduced pressure, 50mL acetic acid was slowly added thereto, and then heated to reflux for 12 hours. Subsequently, after the temperature was reduced to room temperature, acetic acid was vacuum distilled, thereby obtaining the compound represented by Chemical Formula 2.

[0155] Chemical formula 2

[0156]

[0157] Synthesis Example 2: Synthesis of the compound represented by Chemical Formula 3

[0158] The compound represented by Chemical Formula 3 was obtained in substantially the same manner as in Synthesis Example 1, except that a 1 M THF solution (62.3 mmol) of benzylmagnesium chloride was used instead of a 1 M THF solution of 2-butanone-3-magnesium bromide.

[0159] Chemical formula 3

[0160]

[0161] Synthesis Example 3: Synthesis of the compound represented by Chemical Formula 4

[0162] In 250mL 2 neck round bottom flask, with Ph SnCl (20 grams, 51.9mmol) is dissolved in 100mL anhydrous tetrahydrofuran (THF), and then in ice bath, is cooled to 0 ℃, and slowly drips the 1M THF solution (62.3mmol) of 2-methyl-1-butene-3-magnesium bromide wherein.When dripping is finished, at room temperature mixture is stirred 12 hours.After under reduced pressure distillation, the product thus obtained is dissolved in 50mL CH Cl In, at-78 ℃, in 30 minutes, slowly drips 2M HCl diethyl ether solution (155.7mmol), and then at room temperature stirred 12 hours, and solvent is concentrated and vacuum distilled. Subsequently, after the obtained product was dissolved in 50 mL of CH2Cl2, Ag-acetylacetone (103.8 mmol) and Ag-tert-butoxide (51.9 mmol) were added dropwise thereto at 0°C to produce a solid, and after the solid was removed by filtration, the filtrate thus obtained was distilled to obtain the compound represented by Chemical Formula 4.

[0163] Chemical formula 4

[0164]

[0165] Comparative Synthesis Example 1

[0166] 25 mL of acetic acid was slowly added dropwise to tert-butyltriphenyltin compound (10 g, 25.6 mmol) at room temperature, and then heated under reflux at 110° C. for 24 hours. Subsequently, after the temperature was lowered to room temperature, acetic acid was vacuum distilled to obtain a compound represented by Chemical Formula 5.

[0167] Chemical formula 5

[0168]

[0169] Preparation of semiconductor photoresist composition

[0170] Examples 1 to 3 and Comparative Example 1

[0171] The compounds represented by Chemical Formula 2 to Chemical Formula 5 obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 were respectively dissolved in 3 wt % 4-methyl-2-pentanol and filtered through a 0.1 μm polytetrafluoroethylene (PTFE) syringe filter to prepare a photoresist composition.

[0172] A 4-inch diameter circular silicon wafer having a native oxide surface was used as a substrate for thin film deposition. Prior to depositing the resist film, the wafer was treated in a UV ozone cleaning system for 10 minutes, the resist composition was spin-coated on the wafer at 1500 rpm for about 30 seconds, and baked at 100° C. for 120 seconds to form (or provide) a thin film. Thereafter, the film thickness after coating and firing was measured using ellipsometry, wherein the thickness was about 20 nm for Examples 1 to 3 and Comparative Example 1.

[0173] Evaluation: Contrast performance

[0174] The substrate on which the resist film was deposited was exposed to an electron beam with an accelerating voltage of about 100 kV to form (or provide) nanowires having a half pitch of about 40 nm. The irradiated substrate was exposed to 40° C. for 30 seconds, immersed in 2-heptanone in a petri dish for 60 seconds and taken out therefrom, washed with the same solvent for 10 seconds, and finally fired at 150° C. to complete a patterned wafer. The thickness of each exposure area of ​​the patterned wafer was measured to obtain a contrast curve, and the contrast performance γ (contrast) was calculated from the contrast curve, and the results are shown in Table 1.

[0175] γ(contrast)=1 / log(D0 / D 100 )

[0176] D 100 =Exposure dose at which 100% photoresist (PR) begins to remain

[0177] D0 = exposure dose when PR is completely removed

[0178] (Table 1)

[0179] γ(contrast) Example 1 5.7 Example 2 6.8 Example 3 4.8 Comparative Example 1 3.9

[0180] Referring to Table 1, if the photoresist compositions of Examples 1 to 3 are applied (for example, when the photoresist compositions of Examples 1 to 3 are applied), excellent or suitable removal capability of the metal-containing photoresist layer and excellent or suitable pattern characteristics with improved contrast performance are achieved compared to if the photoresist composition of Comparative Example 1 is applied (for example, when the photoresist composition of Comparative Example 1 is applied).

[0181] In the above, certain embodiments of the present disclosure have been described and illustrated. However, it is obvious to those skilled in the art that the present disclosure is not limited to the one or more embodiments described, but various modifications and changes can be made without departing from the spirit and scope of the present disclosure. Therefore, the modified or changed embodiments themselves may not be understood separately from the technical ideas and aspects of the present disclosure, and the modified embodiments are within the scope of the claims of the present disclosure and their equivalent forms.

Claims

1. A semiconductor photoresist composition comprising: an organometallic compound represented by Chemical Formula 1; and Solvents, Chemical formula 1 In Chemical Formula 1, M is one selected from a tetravalent metal, a pentavalent metal, and a hexavalent metal, R 1 for Substituted or unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, Substituted or unsubstituted C6 to C30 aryl, L a -OR a , where L a is a single bond, or a substituted or unsubstituted C1 to C20 alkylene group, and R a is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, or C(O)-R b , where R b is hydrogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C30 aryl, R 2 to R 4 are each independently hydrogen, Substituted or unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C3 to C20 cycloalkyl, 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, C(O)-R c , where R c is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, P(O)OR d R e , where R d and R e are each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, P(O)OR f OR g , where R f and R g are each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, S(O)R h , where R h is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, or S(O)2R i , where R i is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, R 2 to R 4 At least one of a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, C(O)-R c , where R c is hydrogen, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C30 aryl, P(O)OR d R e , where R d and R e are each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, P(O)OR f OR g , where R f and R g are each independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, S(O)R h , where R h is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, or S(O)2R i , where R i is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group; and / or R 2 to R 4 Adjacent groups therein are connected to each other to form a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, X is halogen, OL b -C(O)-R j , where L b is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C2 to C20 alkenylene group, and R j 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, or a combination thereof, or -NR k R l , where R k and R l 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, or a combination thereof, -NR m (COR n ), where R m and R n 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, or a combination thereof, or -NR o C(NR p )R q , where R o , R p and R q 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, or a combination thereof, n1 and m1 are each independently an integer from 1 to 5, p is an integer from 0 to 4, and 4≤n1+m1+p≤6.

2. The semiconductor photoresist composition according to claim 1, wherein M is one selected from Sn, Sb, I, Te, In, Ag, Ni, Bi and Po.

3. The semiconductor photoresist composition according to claim 1, wherein M is Sn.

4. The semiconductor photoresist composition according to claim 1, wherein R 2 to R 4 At least one of Substituted or unsubstituted phenyl, Substituted or unsubstituted tolyl, Substituted or unsubstituted xylyl, C(O)-R c , where R c is 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl, C(R r )=C(R s )(R t ), where R r , R s and R t each independently represents 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl, P(O)OR d R e , where R d and R e each independently represents a 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl, P(O)OR f OR g , where R f and R g each independently represents a 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl, S(O)R h , where R h 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl, or S(O)2R i , where R i 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, substituted or unsubstituted phenyl, substituted or unsubstituted tolyl, or substituted or unsubstituted xylyl; and / or R 2 to R 4 Adjacent groups therein are connected to each other to form a substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted cyclooctyl, substituted or unsubstituted cyclononyl, or substituted or unsubstituted cyclodecyl.

5. The semiconductor photoresist composition according to claim 1, wherein R 2 to R 4 At least one of them is selected from the substituents listed in Group 1-1; or R 2 to R 4 Adjacent groups among them are connected to each other to form at least one of the cyclic groups listed in Groups 1-2, Group 1-1 Group 1-2 and In Group 1-1 and Group 1-2, * is related to R 2 to R 4 Connected carbon.

6. The semiconductor photoresist composition according to claim 1, wherein R 1 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 2,2-dimethylpropyl, substituted or unsubstituted tert-amyl, 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, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, or a combination thereof, and R a 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 2,2-dimethylpropyl, or a combination thereof.

7. The semiconductor photoresist composition according to claim 1, wherein X is halogen, OL b -C(O)-R j , where L b is a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C2 to C10 alkenylene group, and R j 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, or a combination thereof, -NR k R l , where R k and R l 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, or a combination thereof, -NR m (COR n ), where R m and R n 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, or a combination thereof, or -NR o C(NR p )R q , where R o , R p and R q Each is 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, or a combination thereof.

8. The semiconductor photoresist composition according to claim 1, wherein The organometallic compound is represented by any one of the compounds listed in Group 2, Group 2 9. The semiconductor photoresist composition according to claim 1, wherein The amount of the organometallic compound is 1 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 comprises the following additives: a surfactant, a cross-linking agent, a leveling agent or a combination thereof.

11. A method for forming a pattern, the method comprising: forming an etching target layer on a substrate; coating the semiconductor photoresist composition according to claim 1 on the etching target layer to form a photoresist layer; patterning the photoresist layer to form a photoresist pattern; as well as The etching target layer is etched using the photoresist pattern as an etching mask. 12 . The method of claim 11 , wherein the photoresist pattern is formed by applying light having a wavelength of 5 nm to 150 nm.

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