Pattern formation method

Abstract

This invention provides a pattern formation method that improves exposure characteristics and surface roughness, and prevents wiggling or pattern collapse during development due to pattern refinement. [Solution] A step of forming an etching target film on a substrate; A step of forming a photoresist film by spin-coating a semiconductor photoresist composition containing an organometallic compound and a solvent onto the aforementioned film to be etched; A step of exposing the photoresist film using a patterned mask; The step of forming a photoresist pattern by dry developing the photoresist film using a gas; and, This invention relates to a pattern formation method that includes the step of etching the film to be etched using the aforementioned photoresist pattern as an etching mask.

Description

[Technical Field] 【0001】 This document describes a pattern formation method. [Background technology] 【0002】 EUV (extreme ultraviolet) lithography is attracting attention as one of the key technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technique that uses EUV light with a wavelength of 13.5 nm as the exposure light source. It has been demonstrated that EUV lithography can form extremely fine patterns (for example, less than 20 nm) in the exposure process of semiconductor device manufacturing. 【0003】 Extreme ultraviolet (EUV) lithography requires the development of compatible photoresists capable of spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists are striving to meet the specifications for resolution, photospeed, feature roughness, and line edge roughness (LER) for next-generation devices. 【0004】 The intrinsic image blur caused by acid-catalyzed reactions in these polymer-type photoresists limits resolution at small feature sizes, a fact long known in electron beam lithography. Chemically amplified (CA) photoresists, while designed for high sensitivity, can experience further difficulties, partly under EUV exposure, because their typical elemental makeup reduces the absorbance of the photoresists at a wavelength of 13.5 nm, thereby decreasing their sensitivity. 【0005】 CA photoresists may also experience difficulties due to roughness issues at small feature sizes, and experiments have shown that line edge roughness (LER) increases due to a decrease in photospeed, partly due to the nature of the acid-catalyzed process. Due to the shortcomings and problems of CA photoresists, the semiconductor industry has a demand for new types of high-performance photoresists. 【0006】 To overcome the shortcomings of the aforementioned chemically amplified organic photosensitive compositions, inorganic photosensitive compositions have been studied. Inorganic photosensitive compositions are mainly used for negative tone patterning that is resistant to removal by developer compositions through chemical modification via a non-chemical amplification mechanism. Inorganic compositions contain inorganic elements that have a higher EUV absorption rate compared to hydrocarbons, and sensitivity can be ensured even with a non-chemical amplification mechanism. They are also known to be less sensitive to the stochastic effect and have fewer line edge roughness and defects. 【0007】 Inorganic photoresists based on tungsten and tungsten peroxopolyacids mixed with niobium, titanium, and / or tantalum have been reported for use as radiation-sensitive materials for patterning (US5061599; H. Okamoto, T. Iwayanagi, K. Mochiji, H. Umezaki, T. Kudo, Applied Physics Letters, 49(5), 298-300, 1986). 【0008】 These materials have been effective in patterning large features in a bilayer configuration as deep UV, X-ray, and electron beam sources. More recently, impressive performance has been shown when using cationic hafnium metal oxide sulfate (HfSOx) materials with a peroxo complexing agent to image 15 nm half-pitch (HP) by projection EUV exposure (US2011-0045406; JKStowers, A. Telecky, M. Kocsis, BL Clark, DAKEszler, A. Grenville, CN Anderson, PPNaulleau, Proc. SPIE, 7969, 796915, 2011). This system exhibits the best performance of non-CA photoresists and has a light speed that approaches the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials containing peroxo-complexing agents have several practical drawbacks. Firstly, these materials are coated with a highly corrosive sulfuric acid / hydrogen peroxide mixture, resulting in poor shelf-life stability. Secondly, structural modifications to improve performance are not easy as a composite mixture. Thirdly, they must be developed with extremely high concentrations of TMAH (tetramethylammonium hydroxide) solutions, such as 25 wt%. 【0009】 Recently, tin-containing molecules have been found to exhibit excellent extreme ultraviolet absorption, and are being actively researched. In the case of organotin polymers, one such polymer, the alkyl ligand dissociates due to light absorption or the secondary electrons generated by it, and negative tone patterning is possible through crosslinking via oxo bonds with surrounding chains, which prevents removal by organic developers. While such organotin polymers have shown a dramatic improvement in sensitivity while maintaining resolution and line edge roughness, further improvements to the aforementioned patterning properties are necessary for commercialization. [Overview of the Initiative] [Means for solving the problem] 【0010】 One embodiment provides a pattern formation method that improves exposure characteristics and surface roughness, and prevents wiggling or pattern collapse during development due to pattern refinement. 【0011】 A pattern formation method according to one embodiment may include the steps of: forming an etching target film on a substrate; forming a photoresist film by spin-coating a semiconductor photoresist composition containing an organometallic compound and a solvent onto the etching target film; exposing the photoresist film using a patterned mask; forming a photoresist pattern by dry developing the photoresist film using a gas; and etching the etching target film using the photoresist pattern as an etching mask. 【0012】 One embodiment of the pattern formation method allows for the creation of fine patterns with excellent resolution and reduced bridge defects through dry development. [Brief explanation of the drawing] 【0013】 [Figure 1] This is a cross-sectional view showing the process sequence to illustrate the pattern formation method. [Modes for carrying out the invention] 【0014】 The embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in explaining this description, explanations of functions or configurations that have already been made public will be omitted in order to clarify the gist of this description. 【0015】 To ensure clarity in this description, irrelevant details have been omitted, and the same or similar components are given the same reference numerals throughout the specification. Furthermore, the dimensions and thicknesses of each component shown in the drawings are provided arbitrarily for illustrative purposes and are not necessarily limited to those shown in this description. 【0016】 In the drawings, thicknesses were enlarged to clearly represent various layers and regions. Furthermore, for ease of explanation, the thicknesses of some layers and regions were exaggerated in the drawings. When a layer, film, region, plate, or other part is described as being "on top of" or "above" another part, this includes not only cases where it is "directly above" another part, but also cases where another part lies in between. 【0017】 In this description, "substituted" means that the hydrogen atom is substituted with deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 haloalkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, or a cyano group. "Unsubstituted" means that the hydrogen atom is not substituted with another substituent and remains as a hydrogen atom. 【0018】 In this document, "alkyl group" refers to a linear or branched aliphatic hydrocarbon group unless otherwise defined. An alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds. 【0019】 The alkyl group may be a C1 to C20 alkyl group. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, a C1 to C4 alkyl group means that the alkyl chain contains 1 to 4 carbon atoms and is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, and t-butyl. 【0020】 The aforementioned alkyl group refers to specific examples such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. 【0021】 In this document, unless otherwise defined, "cycloalkyl group" refers to a monovalent cyclic aliphatic hydrocarbon group. 【0022】 In this document, unless otherwise defined, "alkenyl group" refers to an aliphatic unsaturated alkenyl group that contains one or more double bonds as a linear or branched aliphatic hydrocarbon group. 【0023】 In this document, unless otherwise defined, "alkynyl group" refers to an aliphatic unsaturated alkynyl group that contains one or more triple bonds as a linear or branched aliphatic hydrocarbon group. 【0024】 In this description, "aryl group" refers to a substituent in which all elements of the cyclic substituent have p-orbitals, and these p-orbitals form a conjugation, and includes monocyclic or fused polycyclic (i.e., rings having adjacent pairs of carbon atoms separated) functional groups. 【0025】 The following describes a pattern formation method according to one embodiment, with reference to the drawings. 【0026】 A pattern formation method according to one embodiment may include the steps of: forming an etching target film on a substrate; forming a photoresist film by spin-coating a semiconductor photoresist composition containing an organometallic compound and a solvent onto the etching target film; exposing the photoresist film using a patterned mask; forming a photoresist pattern by dry developing the photoresist film using a gas; and etching the etching target film using the photoresist pattern as an etching mask. 【0027】 When pattern miniaturization is applied to develop unexposed areas using the conventional wet development process, if a high photoresist selectivity ratio is not met, the pattern cannot withstand the surface tension of the developer, resulting in pattern collapse during development and making it difficult to form the desired pattern. 【0028】 However, in the pattern formation method according to the present invention, by applying a dry development process using gas instead of the conventional wet development process, it is possible to prevent wiggling or pattern collapse due to pattern finening during development. 【0029】 More specifically, the pattern formation method according to the present invention will be described below with reference to Figure 1. 【0030】 Referring to Figure 1(a), the first step is to provide an object to be etched. An example of the object to be etched is a thin film 102 formed on a semiconductor substrate 100. The following explanation will be limited to the case where the object to be etched is a thin film 102. To remove contaminants and other materials remaining on the thin film 102, the surface of the thin film 102 is cleaned. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film. 【0031】 Next, a resist underlayer forming composition for providing a resist underlayer 104 on the surface of the cleaned thin film 102 is coated using a spin-coating method. However, this embodiment is not necessarily limited to this, and various known coating methods, such as spray coating, dip coating, knife-edge coating, and printing methods, such as inkjet printing and screen printing, can also be used. 【0032】 The above-mentioned resist underlayer coating process can be omitted, and the following description will focus on the case where the resist underlayer is coated. 【0033】 Subsequently, drying and baking processes are performed to form a resist underlayer film 104 on the thin film 102. The baking process is carried out at approximately 100 to approximately 500°C, for example, at approximately 100°C to approximately 300°C. 【0034】 The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106. When survey lines reflected from the interface between the substrate 100 and the photoresist film 106 or from the interlayer hard mask are scattered into unintended photoresist regions, this prevents non-uniformity of the photoresist linewidth and interference with pattern formation. 【0035】 Referring to Figure 1(b), a semiconductor photoresist composition is spin-coated onto the etching target film including the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be in a form obtained by coating a thin film 102 formed on the substrate 100 with the semiconductor photoresist composition and then curing it through a heat treatment process. 【0036】 More specifically, the step of forming a pattern using a semiconductor photoresist composition may include the steps of applying the aforementioned semiconductor photoresist composition by spin coating onto a substrate 100 on which a thin film 102 is formed, and drying the applied semiconductor photoresist composition to form a photoresist film 106. 【0037】 As an example, the semiconductor photoresist composition may contain an organometallic compound represented by the following chemical formula 1, and a solvent. 【0038】 [ka] 【0039】 In the aforementioned chemical formula 1, R 1 These are selected from substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 alkenyl groups, substituted or unsubstituted C2 to C20 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, and substituted or unsubstituted C7 to C30 arylalkyl groups. R 2 ~R 4 These are, independently, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C20 cycloalkyl groups, substituted or unsubstituted C2 to C20 alkenyl groups, substituted or unsubstituted C2 to C20 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C7 to C30 arylalkyl groups, alkoxy and aryloxy (-OR) groups. b Herein, R b (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a carboxyl group (-O(CO)Rc , R c is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an alkylamide or a dialkylamide (-NR d R e , wherein R d and R e are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amidato (-NR f (COR g ), wherein R f and R g are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), an amidinato (-NR h C(NR i )R j , wherein R h , R i and R jEach of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR k Herein, R k (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a thiocarboxyl group (-S(CO)R l , R l (which is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) or a dithiocarboxyl group (S(CS)R m , R m (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or substituted C2-C20 alkaiyl groups, substituted or unsubstituted C1-C20 alkoxy groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C1-C20 amine groups, or combinations thereof.) R 2 ~R 4 At least one of them is an alkoxy and an aryloxy (-OR b Herein, R b(which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkaiyl groups, substituted or unsubstituted C1-C20 alkoxy groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R c , R c (which is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylamide or dialkylamide (-NR d R e Herein, R d and R e Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR f (COR g ), here, R f and R g Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinate (-NR h C(NR i )R j Herein, Rh , R i and R j Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), alkylthio and arylthio (-SR k Herein, R k (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a thiocarboxyl group (-S(CO)R l , R l (which is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) and a dithiocarboxyl group (S(CS)R m , R m (is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkaiyl groups, substituted or unsubstituted C1-C20 alkoxy groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C1-C20 amine groups, or a combination thereof). 【0040】 As a specific example, R 1This may be selected from substituted or unsubstituted C1 to C10 alkyl groups, substituted or unsubstituted C3 to C10 cycloalkyl groups, substituted or unsubstituted C2 to C10 alkenyl groups, substituted or unsubstituted C2 to C10 alkynyl groups, substituted or unsubstituted C6 to C12 aryl groups, and substituted or unsubstituted C7 to C20 arylalkyl groups. 【0041】 For example, the R 1 This group may be a methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propanyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethoxy group, propoxy group, or a combination thereof. 【0042】 For example, the aforementioned R 2 ~R 4 At least one of them is alkylthio and arylthio (-SR k Herein, R k (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a thiocarboxyl group (-S(CO)R l , R l(which is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) and a dithiocarboxyl group (S(CS)R m , R m (These may be selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkaiyl groups, substituted or unsubstituted C1-C20 alkoxy groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C1-C20 amine groups, or a combination thereof.) 【0043】 As another example, the semiconductor photoresist composition may include a first organometallic compound, a second organometallic compound, and a solvent. 【0044】 The first organometallic compound is R of the chemical formula 1. 2 ~R 4 At least one of them is alkylthio and arylthio (-SR k Herein, R k (which is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a thiocarboxyl group (-S(CO)R l , R l(which is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) and a dithiocarboxyl group (S(CS)R m , R m (which is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkaiyl groups, substituted or unsubstituted C1-C20 alkoxy groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C1-C20 amine groups, or a combination thereof) The second organometallic compound is R of the chemical formula 1. 2 ~R 4 At least one of them is an alkylamide or dialkylamide (-NR d R e Herein, R d and R e Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR f (COR g ), here, R f and R gEach of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and amidinate (-NR) h C(NR i )R j Herein, R h , R i and R j Each of these may be independently selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof. 【0045】 For example, the first organometallic compound may be represented by the following chemical formula 1A, and the second organometallic compound may be represented by the following chemical formula 1B. 【0046】 [ka] 【0047】 [ka] 【0048】 In the aforementioned chemical formulas 1A and 1B, R 1is selected from a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C7-C30 arylalkyl group, A 1 to A 3 each independently is alkylthio and arylthio (-SR k , wherein, R k is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), a thiocarboxyl group (-S(CO)R l , R l is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof) and a dithiocarboxyl group (S(CS)R m , R m is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C1-C20 amine group, or a combination thereof) and is selected from among B 1 to B 3 each independently is alkylamide or dialkylamide (-NR d Re Herein, R d and R e Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidato (-NR f (COR g ), here, R f and R g Each of these is independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), and amidinate (-NR) h C(NR i )R j Herein, R h , R i and R j Each of these may be independently selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkaiyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof. 【0049】 By mixing two or more organometallic compounds with different ligands, hardening of non-exposed areas can be suppressed and the bridge margin can be improved. Furthermore, by reducing crystallinity through the introduction of various ligands, excellent coating properties and low-level emission reduction (LER) can be achieved. 【0050】 The first organometallic compound and the second organometallic compound may be present in a weight ratio of 1:99 to 99:1. 【0051】 R in one embodiment 1 These are selected from substituted or unsubstituted C1 to C10 alkyl groups, substituted or unsubstituted C3 to C10 cycloalkyl groups, substituted or unsubstituted C2 to C10 alkenyl groups, substituted or unsubstituted C2 to C10 alkynyl groups, substituted or unsubstituted C6 to C12 aryl groups, and substituted or unsubstituted C7 to C20 arylalkyl groups. R d , R e , R f , R g , R h , R i , R j , R k , and R l These can each be independently a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C8 alkenyl group, a substituted or unsubstituted C2-C8 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof. 【0052】 In one specific embodiment, the R 1 These are methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propanyl group, butynyl group, phenyl group, tolyl group, xylene group, benzyl group, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, ethoxy group, propoxy group, or combinations thereof. R d , R e , R f , R g , R h , R i , Rj , R k , and R l Each of these groups can independently be an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propanyl group, a butynyl group, a phenyl group, a tolyl group, a xylene group, a benzyl group, or a combination thereof. 【0053】 For example, the first organometallic compound may be at least one selected from the compounds listed in Group 1 below. 【0054】 [ka] 【0055】 The second organometallic compound may be at least one selected from the compounds listed in Group 2 below. 【0056】 [ka] 【0057】 The semiconductor photoresist composition may further contain at least one other additive selected from surfactants, dispersants, hygroscopic agents, and coupling agents. 【0058】 The surfactant can improve the coating uniformity and wettability of the photoresist composition. In exemplary examples, the surfactant may consist of, but is not limited to, sulfate esters, sulfonates, phosphate esters, soaps, amine salts, quaternary ammonium salts, polyethylene glycol, alkylphenol ethylene oxide adducts, polyhydric alcohols, nitrogen-containing vinyl polymers, or combinations thereof. For example, the surfactant may include alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, or quaternary ammonium salts. If the photoresist composition contains the surfactant, the surfactant may be present in an amount of about 0.001% to about 3% by weight based on the total weight of the photoresist composition. 【0059】 The dispersant can serve to ensure that the constituent components of the photoresist composition are uniformly dispersed within the photoresist composition. In exemplary examples, the dispersant may consist of, but is not limited to, epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, glucose, sodium dodecyl sulfate, sodium silate, oleic acid, linoleic acid, or a combination thereof. If the photoresist composition contains the dispersant, the dispersant may be present in an amount of about 0.001% to about 5% by weight based on the total weight of the photoresist composition. 【0060】 The hygroscopic agent can play a role in preventing the photoresist composition from being negatively affected by moisture. For example, the hygroscopic agent can play a role in preventing the metal contained in the photoresist composition from being oxidized by moisture. The hygroscopic agent in exemplary examples may consist of, but is not limited to, polyoxyethylene nonylphenol ether, polyethylene glycol, polypropylene glycol, polyacrylamide, or a combination thereof. If the photoresist composition contains the hygroscopic agent, the hygroscopic agent may be present in an amount of about 0.001% to about 10% by weight based on the total weight of the photoresist composition. 【0061】 The coupling agent can play a role in improving the adhesion between the photoresist composition and the underlying film when the photoresist composition is coated onto the underlying film. The coupling agent in the exemplary examples may include a silane coupling agent. The silane coupling agent may consist of, but is not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxpropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, or trimethoxy[3-(phenylamino)propyl]silane. When the photoresist composition contains the coupling agent, the coupling agent may be present in an amount of about 0.001% to about 5% by weight based on the total weight of the photoresist composition. 【0062】 Next, a first baking step is performed in which the substrate 100 on which the photoresist film 106 is formed is heated. The first baking step can be performed at a temperature of approximately 80°C to approximately 120°C. 【0063】 Referring to Figure 1(c), the photoresist film 106 is selectively exposed using a patterned mask 110. 【0064】 As an example, examples of light used in the exposure process include light with high energy wavelengths of 3 to 15 nm, such as EUV (Extreme Ultra Violet; wavelength 13.5 nm) and E-Beam (electron beam). 【0065】 The exposed region 106b of the photoresist film 106 forms a polymer through crosslinking reactions such as condensation between organometallic compounds, resulting in a different solubility from the unexposed region 106a of the photoresist film 106. 【0066】 Next, a second baking process is performed on the substrate 100. The second baking process can be carried out at a temperature of approximately 90°C to approximately 200°C. By performing the second baking process, the exposed region 106b of the photoresist film 106 becomes less soluble in the developer. 【0067】 Next, a step may be performed in which a photoresist pattern is formed by developing the photoresist film. 【0068】 Figure 1(d) shows the photoresist pattern 108 formed by removing the photoresist film 106a corresponding to the unexposed region by development. Specifically, the photoresist pattern 108 corresponding to the negative tone image is completed by removing the photoresist film 106a corresponding to the unexposed region by dry development using gas. 【0069】 Such a dry development step can be carried out by using a pure plasma (high pressure, low power) or thermal process while flowing a dry developing chemical such as BCl3 (boron trichloride) or another Lewis acid. In some examples, BCl3 can rapidly remove the photoresist film 106a corresponding to the unexposed areas, leaving exposed areas 106b that may be transferred to the underlying layers by plasma substrate etching processes, for example, conventional etching processes. 【0070】 Plasma processes include TCP (Transformer Coupled Plasma), ICP (Inductively Coupled Plasma), or CCP (Capacitively Coupled Plasma), and can employ equipment and techniques known in the industry. For example, the process may be carried out at an overpressure of 5 mT (e.g., over 15 mT) and a power level of less than 1000 W (e.g., less than 500 W). Temperatures can be 0 to 300°C (e.g., 30 to 120°C) at a flow rate of 100 to 1000 sccm (standard cubic centimeters per minute), for a period of 1 to 3000 seconds (e.g., 10 to 600 seconds), for a flow rate of approximately 500 sccm. 【0071】 In thermal developing processes, the substrate is exposed to a dry developing chemical (e.g., Lewis acid) in a vacuum chamber (e.g., an oven). Suitable chambers may include a vacuum line, a dry developing chemical gas (e.g., BCl3) line, and heaters for temperature control. In some embodiments, the interior of the chamber may be coated with corrosion-resistant films such as organic polymers or inorganic coatings. One such coating is polytetrafluoroethylene ((PTFE), e.g., Teflon 1M). Such materials can be used in the thermal processes of this technique without the risk of removal by plasma exposure. 【0072】 In various embodiments, the method of this technology combines all dry stages of film formation by vapor deposition, (EUV) lithographic photopatterning, and dry development. In such processes, the substrate can also be moved directly to the dry development / etching chamber following photopatterning with an EUV scanner. The dry development of this technology can also offer various advantages over wet development known in the industry. For example, it can be advantageous in achieving smaller pitches by eliminating line collapse due to surface tension in wet development and by eliminating the use of organic solvents. 【0073】 As explained earlier, the line and space line widths in a line / space = 1:1 pattern of the photoresist pattern 108 formed after exposure and dry development using high-energy wavelength light such as EUV (Extreme Ultra Violet; wavelength 13.5 nm) and E-Beam (electron beam) can independently range from 5 nm to 100 nm. For example, the line and space line widths may be 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, 5 nm to 20 nm, and 5 nm to 10 nm. 【0074】 Next, the photoresist pattern 108 is used as an etching mask to etch the resist underlayer film 104. This etching process forms an organic film pattern 112. The formed organic film pattern 112 can have a width corresponding to the photoresist pattern 108. 【0075】 Referring to Figure 1(e), the photoresist pattern 108 is applied as an etching mask to etch the exposed thin film 102. As a result, the thin film is formed with the thin film pattern 114. 【0076】 The thin film 102 can be etched, for example, by dry etching using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl3, or a mixture thereof. 【0077】 In the previously performed exposure process, the thin film pattern 114 formed using the photoresist pattern 108, which was formed by the exposure process using an EUV light source, can have a width corresponding to the photoresist pattern 108. For example, it can have a width of 5 nm to 100 nm, similar to the photoresist pattern 108. For instance, the thin film pattern 114 formed by the exposure process using an EUV light source can have a width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm, similar to the photoresist pattern 108, and more specifically, it may be formed with a width of 20 nm or less. [Examples] 【0078】 The present invention will be described in more detail below through examples of pattern formation methods. However, the technical features of the present invention are not limited by the following examples. 【0079】 (Synthesis of organometallic compounds) Synthesis Example 1 Dissolve 25 g (102.03 mmol, 5.2 g) of LiNMe in anhydrous hexane in a 100 mL round-bottom flask and cool the flask to -78°C. Slowly add 8.2 g (34.01 mmol, 10 g) of isopropyltin trichloride dropwise, and react at room temperature for 24 hours. After the reaction is complete, filter and concentrate the mixture, then vacuum dry to obtain the organometallic compound shown in chemical formula 6 below. 【0080】 [ka] 【0081】 Synthesis Example 2 In a 1 L round-bottom flask, dissolve iPrSn(NEt2)3 (18.9 g, 50 mmol) in 500 mL of anhydrous hexane and cool the flask to -78°C. Slowly add N-Methylacetamide (11 g, 150 mmol) dropwise, then react at room temperature for 24 hours. After the reaction is complete, concentrate the mixture and vacuum dry it to obtain the organometallic compound shown in chemical formula 7 below. 【0082】 [ka] 【0083】 Synthesis Example 3 In a 1 L round-bottom flask, dissolve iPrSn(NEt2)3 (18.9 g, 50 mmol) in 500 mL of anhydrous hexane and cool the flask to -78°C. Slowly add 2-Methyl-2-propanethiol (13.53 g, 150 mmol) dropwise, then react at room temperature for 24 hours. After the reaction is complete, concentrate the mixture and vacuum dry it to obtain the organometallic compound shown in chemical formula 8 below. 【0084】 [ka] 【0085】 Synthesis Example 4 After dissolving 10 g of the organotin compound shown in chemical formula A below in 30 ml of toluene, 8 g of 2-methoxyethanethioic S-acid is slowly added, and the mixture is stirred at room temperature (20 ± 5 °C) for 6 hours. Subsequently, the toluene and the separated propionic acid are removed by vacuum distillation to obtain the organometallic compound shown in chemical formula 9 below. 【0086】 [ka] 【0087】 Synthesis Example 5 Dissolve 20g (51.9 mmol) of Ph3SnCl in 70ml of THF in a 250mL two-necked round-bottom flask, and lower the temperature to 0°C using an ice bath. Then, slowly add 1M tatobutylmagnesium chloride (tBuMgCl) THF solution (62.3 mmol) dropwise. After the dropwise addition is complete, stir at room temperature (25±3°C) for 12 hours to obtain the t-BuSnPh3 compound. 【0088】 Subsequently, t-BuSnPh3 (10 g, 24.6 mmol) is dissolved in 50 mL of CH2Cl2, and 3 t equivalents (73.7 mmol) of 2 M HCl diethyl ether solution are slowly added dropwise at -78°C for 30 minutes. After stirring at room temperature for 12 hours, the solvent is concentrated and the t-BuSnCl3 compound is obtained by vacuum distillation. 【0089】 Subsequently, 32 mL of propionic acid is slowly added dropwise to t-BuSnCl3 (10 g, 25.6 mmol) at room temperature, and the mixture is heated under reflux for 12 hours. After raising the temperature to room temperature, the propionic acid is vacuum-distilled to obtain the organometallic compound shown in chemical formula 10 below. 【0090】 [ka] 【0091】 Manufacturing Examples 1 to 9: Manufacturing of compositions for semiconductor photoresists Semiconductor photoresist compositions containing organometallic compounds obtained from Synthesis Examples 1 to 5 were prepared as shown in Table 1 below. 【0092】 Each compound was dissolved in 4-methyl-2-pentanol at a concentration of 3 wt%, filtered through a 0.1 μm PTFE Syringe filter, and a 4-inch diameter circular silicon wafer with a native-oxide surface was used as a substrate for thin film deposition. Before deposition of the resist thin film, the wafer was treated with a UV ozone cleaning system for 10 minutes. The resist composition was then spin-coated onto the wafer at 1500 rpm for 30 seconds and baked at 100°C for 120 seconds to form a thin film. Subsequently, the thickness of the coated and baked film was measured via ellipsometry and found to be approximately 25 nm. 【0093】 [Table 1] 【0094】 Pattern formation Examples 1 to 8 and Comparative Example 1 (Dry Development) A hydrophobic surface was formed on an 8-inch silicon wafer by spin-coating it with hexamethyldisilazane (HMDS). Then, the metal-containing photoresist PR composition according to Production Examples 1 to 9 was spin-coated onto the wafer at 1,500 rpm for 30 seconds, and the coated wafer was heat-treated at 160°C for 60 seconds. 【0095】 A grid array of 200 μm x 30 μm rectangular pads was projected onto each coated wafer using EUV light (Lawrence Berkeley National Laboratory Micro Exposure Tool, MET5). The pad exposure time was adjusted to ensure that the increased EUV dose was applied to each pad. 【0096】 Subsequently, the resist and substrate were exposed on a hot plate at 160°C for 90 seconds, followed by post-exposure baking (PEB). 【0097】 The fired film was exposed to hydrogen bromide vapor using dry developing equipment. The hydrogen bromide vapor flow rate was adjusted to a value between 5 and 500 sccm (standard cubic centimeters per minute) to provide a measured chamber pressure of 0.1 torr or 5 torr. The wafer samples were heated to a temperature of 120°C to 200°C. The heated wafer samples were exposed to flowing hydrogen bromide vapor for various durations ranging from 0 to 600 seconds. The process was completed by removing the unexposed coating areas and forming a negative tone image. 【0098】 Comparative Examples 2 and 3 (wet development) After coating the metal-containing photoresist PR compositions according to Production Example 3 and Production Example 9 and going through the exposure step, instead of dry developing the fired film using dry developing equipment, the film was immersed in a developer (2-heptanone) for 30 seconds, and then washed with the same developer for an additional 10 seconds to remove the unexposed coated areas and form a negative tone image. Finally, the process was completed by heat treatment at 150°C for 1 minute. 【0099】 Evaluation: Characterization of pattern bridges After measuring the average line width for each field along the dose range scanned using a CD-SEM (CG4100, Hitachi) for the resist patterns formed from Examples 1 to 8 and Comparative Examples 1 to 3, the presence or absence of bridge defects (defects) on the substrate by pattern line width size was confirmed via the scanning electron microscope image, and the results are shown in Table 2. 【0100】 If there is no bridge defect, it is indicated as "X"; if there is a bridge defect, it is indicated as "○". 【0101】 [Table 2] 【0102】 Referring to Table 2, it can be confirmed that the pattern formation methods according to Examples 1 to 8 have superior resolution compared to the pattern formation methods according to Comparative Examples 1 to 3, and form patterns without bridge defects. 【0103】 As described above, specific embodiments of the present invention have been explained and illustrated, but it is obvious to those ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Accordingly, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the invention, and the modified embodiments should fall within the scope of the claims of the present invention. [Explanation of Symbols] 【0104】 100: Substrate, 102: Thin film, 104: Resist underlayer, 106: Photoresist film, 106a: Unexposed area, 106b: Exposed area, 108: Photoresist pattern, 110: Patterned mask, 112: Organic film pattern, 114: Thin film pattern.

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