Tin compounds containing tin-oxygen double bonds and photoresist compositions containing the same

Abstract

To provide a tin compound including a tin-oxygen double bond, a photoresist composition including the same, and a method for forming a photoresist pattern using the same.SOLUTION: There is provided a method for forming a photoresist pattern that includes the step of dissociating an organic ligand of an organometallic compound upon light exposure to cause an addition reaction between metal molecules.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to tin compounds containing tin-oxygen double bonds, photoresist compositions containing the same, and methods of forming photoresist patterns using the same. [Background technology]

[0002] Research into miniaturizing semiconductor patterns, which is essential for manufacturing highly integrated semiconductor devices, continues. Semiconductor miniaturization reached its limits in the early 2000s. Initially, miniaturization was achieved through lithography processes using short-wavelength light sources. However, since the 90nm technology node, innovative technologies have been introduced that not only achieve simple miniaturization but also maintain high performance and low power consumption. The development of lithography technologies such as ArF immersion technology and double patterning has allowed miniaturization to be maintained without changing the light source, but has led to problems such as increased process complexity and costs. In 2020, EUV lithography technology was introduced for mass production of 7nm-class semiconductors, and related research is currently underway.

[0003] Photolithography is the step in semiconductor manufacturing that creates circuits by using light to transfer designs created on a mask onto the surface of a wafer. When exposed to radiation, such as ultraviolet (UV), extreme ultraviolet (EUV), or electron beam radiation, photoresist undergoes a chemical change that creates a pattern. In positive resist, the exposed areas are selectively removed, while in negative resist, the unexposed areas are removed.

[0004] Photoresists are divided into chemically amplified (CAR) and non-chemically amplified types. CARs contain photoacid generators that generate acid in response to light, allowing them to amplify their reaction even with small amounts of light. However, CARs can cause line edge roughness (LER) and non-uniform pattern formation due to stochastic effects. Chemical stochastic effects refer to the randomness that occurs during the reaction process of chemicals within the photoresist, and are influenced by various factors such as reactivity, molecular mobility, and reaction mechanism. Photon stochastics refers to the randomness that occurs from the number and distribution of photons irradiated on the photoresist, and can have large fluctuations, especially at low light exposure levels.

[0005] To solve these problems, inorganic photoresists are being researched. Inorganic photoresists have excellent corrosion resistance and mechanical strength, allowing for stable formation of ultra-fine patterns, and can maintain high sensitivity due to their high EUV absorption rate. In particular, photoresists containing inorganic elements such as tin (Sn), indium (In), and hafnium (Hf) boast better EUV sensitivity and corrosion resistance than conventional organic photoresists.

[0006] Recent studies have shown that tin oxide clusters exhibit high EUV absorption and excellent line edge roughness (LER) characteristics, but further research is still needed to improve EUV sensitivity. The development of such inorganic photoresists is considered a significant technological advancement that overcomes the limitations of conventional organic resists, provides the resolution and sensitivity for the formation of ultra-fine patterns, and solves the problem of pattern collapse. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Korean Patent Publication KR10-2024-0103989 A (2024.07.04) [Patent Document 2] Korean Patent Publication No. 10-2024-0104028 A (2024.07.04) Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present disclosure is to provide novel tin compounds containing a tin-oxygen double bond that have excellent photosensitivity and corrosion resistance.

[0009] An object of the present disclosure is to provide a photoresist composition containing the tin compound.

[0010] Another object of the present disclosure is to provide a method for forming a photoresist pattern that can prevent deterioration in the reproducibility of the photoresist pattern due to the external environment.

[0011] It is still another object of the present disclosure to provide a method for forming a photoresist pattern that can form a high-quality photoresist pattern without reacting with gas molecules. [Means for solving the problem]

[0012] The present disclosure provides tin compounds that are useful as photoresist materials and include a core skeleton containing a tin-oxygen double bond and organic ligands bonded to the core skeleton.

[0013] In one embodiment, the central skeleton may be tin dioxide (O=Sn=O) or tin monoxide (O=Sn), and the organic ligand may be any one or more selected from the group consisting of formic acid, C1-C10 alkyl carboxylate, C2-C10 alkenyl carboxylate, C3-C10 cycloalkyl carboxylate, C6-C20 aryl carboxylate, haloC1-C10 alkyl carboxylate, C1-C10 alkylcarbonyloxy, C2-C10 alkenylcarbonyloxy, C3-C10 cycloalkylcarbonyloxy, C6-C20 arylcarbonyloxy, haloC1-C10 alkylcarbonyloxy, C1-C10 alkylcarbonylamine, and haloC1-C10 alkylcarbonylamine.

[0014] In one embodiment, the tin compound may be represented by the following chemical formulas 1 to 4. [Chemical formula 1] JPEG0007745295000001.jpg37170 [Chemical formula 2] JPEG0007745295000002.jpg37170 [Chemical formula 3] JPEG0007745295000003.jpg23170 [Chemical formula 4] JPEG0007745295000004.jpg14170 (In the above chemical formulas 1 to 4, R1 to R7 are each independently hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl.)

[0015] Specifically, R1 to R4 may be, independently of one another, C1-C5 alkyl or haloC1-C5 alkyl, and R5 to R7 may be, independently of one another, hydrogen, C1-C5 alkyl or haloC1-C5 alkyl.

[0016] The present disclosure also provides a photoresist composition comprising the above-described tin compound.

[0017] The photoresist composition is an inorganic resist for extreme ultraviolet (EUV) and / or electron beam lithography, and upon irradiation with extreme ultraviolet (EUV) or an electron beam, chemical contrast is exhibited through an additive reaction between inorganic components, and a pattern may be formed in an optional development process.

[0018] In particular, the photoresist may be an extreme ultraviolet (EUV) photoresist.

[0019] The present disclosure also provides a method for forming a photoresist pattern, which includes a step in which, upon exposure, the organic ligands of the organometallic compound dissociate and an addition reaction between metal molecules occurs.

[0020] In one embodiment, the method for forming a photoresist pattern may include the steps of: (a) applying a photoresist composition containing an organometallic compound to a substrate to form a thin film; (b) exposing the thin film to light; and (c) developing the exposed thin film using a developer solution.

[0021] In one embodiment, the organometallic compound may include a central skeleton containing a tin-oxygen double bond and organic ligands bonded to the central skeleton.

[0022] In one embodiment, the central skeleton may be tin dioxide (O=Sn=O) or tin monoxide (O=Sn).

[0023] In one embodiment, the exposure in step (b) may be performed by any one selected from an electron beam (E-beam), extreme ultraviolet (EUV), I-line, krypton fluoride (KrF) laser, argon fluoride (ArF) laser, deep ultraviolet (DUV), vacuum ultraviolet (VUV), X-ray, and ion beam. [Effects of the Invention]

[0024] A photoresist composition containing a tin compound according to one embodiment has excellent photosensitivity and corrosion resistance, and a photoresist pattern using the same can be formed with a thin thickness even in an ultra-fine pattern.

[0025] The tin compound according to one embodiment is chemically stable and highly soluble in organic solvents, and can be useful as a photoresist material in a photoresist composition.

[0026] Furthermore, a photoresist composition including a tin compound according to an embodiment can prevent a problem of deterioration in pattern reproducibility due to external environments such as moisture and carbon dioxide when forming a photoresist pattern.

[0027] Furthermore, a photoresist composition containing a tin compound according to one embodiment can form a high-quality photoresist pattern under low exposure dose without reacting with gas molecules, and is therefore industrially very useful. [Brief explanation of the drawings]

[0028] [Figure 1] 1A and 1B are schematic diagrams illustrating the mechanism of a method for forming a photoresist pattern according to an embodiment of the present disclosure. [Figure 2] 1A and 1B are schematic diagrams illustrating the mechanism of a method for forming a photoresist pattern according to an embodiment of the present disclosure. [Figure 3] 1 shows the results of analysis of tin compound 1 obtained in Example 1 using a Maldito-Dietof mass spectrometer (MALDI-TOF MS). [Figure 4] This is the result of estimating the molecular formula for the peak corresponding to (a) in Figure 3 by isotope distribution simulation calculation. [Figure 5] This is the result of estimating the molecular formula for the peak corresponding to (b) in Figure 3 by isotope distribution simulation calculation. [Figure 6] 1 shows the results of photoelectron spectroscopy (XPS) analysis of tin compound 1 obtained in Example 1. [Figure 7]1 shows the results of FD-MS analysis of tin compound 2 obtained in Example 2. [Figure 8] This is the result of estimating the molecular formula for the peak corresponding to (b) in Figure 7 by isotope distribution simulation calculation. [Figure 9] 1 shows the results of FT-IR spectroscopy of tin compound 2 obtained in Example 2. [Figure 10] 1 shows the results of analysis of tin compounds 3-1 and 3-2 obtained in Example 3 using a Maldietoff mass spectrometer (MALDI-TOF MS). [Figure 11] The peak corresponding to (a) in Figure 10 is the result of estimating the molecular formula by isotope distribution simulation calculation. [Figure 12] The peak corresponding to (b) in Figure 10 is the result of estimating the molecular formula by isotope distribution simulation calculation. [Figure 13] 10 shows the results of observing a pattern irradiated with an exposure dose of 130 mJ / cm 2 in Example 9 using a CD-SEM. [Figure 14] 10 shows the results of observing a pattern irradiated with an exposure dose of 120 mJ / cm 2 in Example 9 using a CD-SEM. [Figure 15] 10 shows the results of observing a pattern irradiated with an exposure dose of 110 mJ / cm 2 in Example 9 using a CD-SEM. [Figure 16] 10 shows the results of observing a pattern irradiated with an exposure dose of 100 mJ / cm 2 in Example 9 using a CD-SEM. [Figure 17] 10 shows the results of observing a pattern irradiated with an exposure dose of 90 mJ / cm 2 in Example 9 using a CD-SEM. [Figure 18] 10 shows the results of observing a pattern irradiated with an exposure dose of 80 mJ / cm 2 in Example 9 using a CD-SEM. [Figure 19] 10 shows the results of observing a pattern irradiated with an exposure dose of 70 mJ / cm 2 in Example 9 using a CD-SEM. [Figure 20] 10 shows the results of observing a pattern irradiated with an exposure dose of 60 mJ / cm 2 in Example 9 using a CD-SEM. [Figure 21]10 shows the results of observing a pattern irradiated with an exposure dose of 50 mJ / cm 2 in Example 9 using a CD-SEM. [Figure 22] 10 shows the results of observing a pattern irradiated with an exposure dose of 40 mJ / cm 2 in Example 9 using a CD-SEM. [Figure 23] 10 shows the results of observing the pattern of an exposure dose of 500 μC / cm 2 in Example 10 with an FE-SEM and an atomic force microscope (AFM). [Figure 24] 1 shows the results of measuring the remaining thickness of the photoresist pattern obtained in Experimental Example 2 according to the exposure dose using an AFM. [Figure 25] 1 shows the results of measuring the remaining thickness of the photoresist pattern obtained in Experimental Example 2 according to the exposure dose using an AFM. [Figure 26] 1 shows the results of measuring the remaining thickness of the photoresist pattern obtained in Experimental Example 2 according to the exposure dose using an AFM. DETAILED DESCRIPTION OF THE INVENTION

[0029] Unless otherwise defined herein, all technical and scientific terms have the same meaning as commonly understood by those skilled in the art to which this invention belongs. The terms used in the description herein are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention.

[0030] Also, as used in the specification and the appended claims, the singular forms "a," "an," and "the" can be intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0031] In addition, the numerical ranges used herein include the lower and upper limits, all values ​​within the range, increments logically derived from the form and width of the defined range, and all possible combinations of the upper and lower limits of the numerical ranges defined in different forms. In the specification of the present invention, unless otherwise specified, values ​​outside the numerical ranges that may occur due to experimental error or rounding off of values ​​are also included in the defined numerical ranges.

[0032] Furthermore, throughout this specification, "comprising," "comprising," "containing," or "having" an element means that it may further include other elements, but does not exclude unrecited elements, materials, or steps, unless specifically stated to the contrary.

[0033] In this specification, "room temperature" may mean a temperature in a state where the temperature is not artificially regulated, and may be, for example, 20°C to 40°C, or 20°C to 30°C, or 23°C to 26°C, or 21°C to 23°C.

[0034] As used herein, the term "alkyl" refers to a saturated, straight-chain or branched, acyclic hydrocarbon having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Representative saturated straight-chain alkyls include -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl, and -n-decyl, while saturated branched alkyls include -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, and the like.

[0035] As used herein, the term "alkenyl" refers to a group derived from a straight or branched chain hydrocarbon containing one or more double bonds.

[0036] In this specification, when it is written as "C1-C10", this means that the number of carbon atoms is 1 to 10. For example, C1-C10 alkyl means alkyl having 1 to 10 carbon atoms.

[0037] As used herein, the terms "halogen" and "halo" mean fluorine, chlorine, bromine, or iodine.

[0038] The term "haloalkyl" as used herein refers to an alkyl group in which one or more hydrogen atoms are replaced with a halogen atom. For example, haloalkyl includes -CF, -CHF, -CHF, -CBr, -CHBr, -CHCI, -CHI, -CHI, -CH-CF, -CH-CHF, -CH-CHF, -CH-CBr, -CH-CHBr, -CH-CHBr, etc., where alkyl and halogen are as defined above.

[0039] As used herein, the term "aryl" refers to a carbocyclic aromatic group containing 5 to 10 ring atoms. Representative examples include, but are not limited to, phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, and the like. Carbocyclic aromatic groups can be optionally substituted.

[0040] As used herein, the term "cycloalkyl" refers to a monocyclic or polycyclic saturated ring containing carbon and hydrogen atoms and no carbon-carbon multiple bonds. Examples of cycloalkyl groups include, but are not limited to, (C3-C10) cycloalkyl (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl). Cycloalkyl groups may be optionally substituted. In one embodiment, the cycloalkyl group is a monocyclic or bicyclic ring.

[0041] As used herein, the terms "carboxylic acid," "carboxyl," and "carboxy" refer to --COOH.

[0042] As used herein, the term "alkyl carboxylate" means (alkyl)-COOH, where carboxylic acid is as defined above.

[0043] The term "alkylcarbonyl" as used herein means -CO-(alkyl), where alkyl is as defined above.

[0044] As used herein, the term "alkylcarbonyloxy" refers to a (alkyl)-CO-O-* radical, where "alkylcarbonyl" is defined above.

[0045] The present disclosure will now be described in detail, but by way of example only, and the present disclosure is not limited to the specific embodiments illustratively described.

[0046] The present disclosure provides tin compounds that include a core structure that includes a tin-oxygen double bond and an organic ligand attached to the core structure.

[0047] The tin compound of the present disclosure can be thermodynamically stabilized by a double bond between the tin atom and the oxygen atom and by the organic ligand bonding to the tin atom. This suppresses dimer formation and allows the compound to exist in a monomolecular form, which can provide excellent photosensitivity and corrosion resistance when used as a photoresist material. Furthermore, a photoresist composition containing the compound can be used to form a photoresist pattern with excellent resolution, edge roughness, and mechanical strength.

[0048] The central skeleton may be tin dioxide (O=Sn=O) or tin monoxide (O=Sn). Tin compounds commonly used in conventional photoresist materials have a Sn-C or Sn-N central skeleton. Upon exposure, the tin atom dissociates from a carbon or nitrogen atom, forming a radical (-Sn·) with an unpaired electron on the tin atom. This radical reacts with moisture and carbon dioxide in the surrounding environment during the photoresist pattern formation process to form -Sn-OH (hydroxyl group) or -Sn-O3CH (carbonate), which then undergo a condensation reaction to form Sn-O-Sn bridges or Sn-(CO3)-Sn bridges. In fact, it is difficult to maintain constant concentrations of moisture and carbon dioxide during semiconductor manufacturing processes, which can lead to problems with reduced photoresist pattern reproducibility.

[0049] However, in the tin compound of the present disclosure, upon exposure, the organic ligand dissociates to generate thermodynamically unstable tin dioxide (O=Sn=O) or tin monoxide (O=Sn) molecules, and these molecules can exist within close proximity due to the volume occupied by the organic ligand. This ensures that a cross-sectional area is sufficient for the addition reaction to occur with only a small amount of thermal energy supplied during exposure.

[0050] In one embodiment, the organic ligand can be a neutral ligand or an anionic ligand, but is not necessarily limited thereto as long as it achieves the objectives of the present disclosure.

[0051] As an example, the neutral ligand may be pyrazole, imidazole, dimethyl sulfide, or the like. sulfide, benzaldehyde, dimethyl sulfoxide (DMSO), pyrrolidine, n-butylamine, aniline, ethylbenzoate, pyrazine, n-propylamine, formamide, benzonitrile, pyrimidine, ethylenediamine, acetamide, methylformamide, t-butylamine, pyridine, propionitrile, triethylamine, ethylamine, diethylamine, pivalic acid, 2-pyrrolidone, water, diglyme, tetrahydrofuran (THF), nitric acid Acid, benzyl alcohol, t-butanol, ethyl benzene, benzoic acid, n-methylpyrrolidone, acetonitrile, furan, diethylformamide, n-propanol, 2-propanol, ethanol, methanol, trifluoroacetic acid, formic acid, dimethylformamide (DMF), 1,4-dioxane (1,The solvent may be any one or more selected from the group consisting of 4-dioxane, dimethylacetamide, benzoic acid, acetic acid, 1-butanol, ethyl acetate, dimethoxyethane, ethylene glycol, methoxyethanol, phenol, and diethyl ether.

[0052] In one example, the anionic ligand is SiO4 4- , pyrazolate - , MeS - , Me2dtc - , N(EtOH)(EtO)2 2- , PhCH2S - , EtOCS 2- , thioacetate - , N(EtOH)2(EtO) - , salicylate 2- , CyS - , i-Pr2dtc - , O-Et-O 2- , MeOCS2 - , SiCl3 - , Py(COO-)3 3- , CH2S2 2- , Et2NCOO - , i-Pr2NCOO - , Si(PhCOO)4 4- , OCS2 2- , H2-citrate - , H-citrate 2- , C.N. - , EtS - , AsO4 3- , AsO3 3- , i-PrO - , Et2dtc - , i-PrS -, pyrrolidine-dtc - , O2 - , PhS. - , o-PhO2 2- , CF3CF2COO - , o-Ph(CH2COO)2 2- , m-Ph(CH2COO)2 2- , citrate 3- , N 3- , PO4 3- , OCN - , t-BuS - , Et-COO - , malate - , n-PrO - , i-ProOCS 2- , NO 2- , glycinate - , SO3 2- , PhCOO - , t-Bu-COO-(pivalate) - , HAsO4 2- , PhO - , SeO3 2- , SCN - , N(CH2COO)3 3- , PhCH2O - , MeOCOO - , MeO - , Ph(COOH)(COO)2 2- , i-Pr-COO - , furandicarboxylate - , N.C.-N.-C.N. - , EtO - , HClC-COO - , HO-Et-O - , m-Ph(COO)2 2- , HPO4 2- , SeCN - , pyrrolate - , H2PO2 2- , p-Ph(CH2COO)2 2- , imidazolate - , S 2- , H.C.O.O. -, Ph(COO)3 3- , o-Ph(COO)2 2- , n-BuO - , CH3COO - , O.H. - , Se 2- , t-BuO - , p-Ph(COO)2 2- , N(EtO)3 3- , MeO-Et-O - , C2O4 2- , Te 2- , Cl3CCOO - , Me3SiO - ,HO-Ph-COO - , CF3CF2CF2COO - , GeCl3 - , Cl - , OTeF5 - , EDTA 4- , n-PrCOO - , CO3 2- , Et(COO)2 2- , S2O3 2- , AlMe4 - , BH3CN - , Et(COOH)(COO - ), Br - , I - , fumarate 2- , (O2N)2PhCOO - , CF3COO - , BH4 - , salicylate - , SnCl3 - , Ph(COOH)2(COO) - , (MeO)2PO2 - , SH - , -OOC-C≡C-COO - , Me2NCOO - , H2PO4 - , lactate - , p-O2NPhO - , saccharinate - , tartrate 2- , C(CN)3 - , SeO4 2-, CH3SO3 - , HCO3 - , SO4 2- , m-Ph(COOH)(COO) - , o-Ph(COOH)(COO) - , p-H2N - pH-SO3 - , Naph(SO3)2 2- , C2O4H - , ClO3 - , H.C.B. 11 H 11 - , F - , NO3 - , PhSO3 - , B(PhO2)2 - , ReO4 - , SiF6 2- , p - Ph(COOH)(COO) - , p-Me-PhSO3 - (OTs), B 10 H 10 2- , BHEt3 - , B(CN)4 - , Picrate, B 12 H 12 2- , H.C.B. 11 H 11 - x Cl x - , H-tartrate - , AlCl4 - , CF3SO3 - (triflate), HSO4 - , (F3C)3C-O - , triflimidate - , GaCl4 - , SbCl6 - , ClO4 - , S2O6 2- , AsF6 - , SbF6 - , BF4 - , I3 - , BH(C6F5)3 - , B(3,5-PhCl2)4- , Al(OC(CF3)3)4 - , BMe(C6F5)3 - , PF6 - , BPh4 - , B(C6F5)4 - and BArF4 - It may be any one or more selected from the group consisting of:

[0053] In one embodiment, the organic ligand may be at least one selected from the group consisting of formic acid, C1-C10 alkyl carboxylate, C2-C10 alkenyl carboxylate, C3-C10 cycloalkyl carboxylate, C6-C20 aryl carboxylate, haloC1-C10 alkyl carboxylate, C1-C10 alkylcarbonyloxy, C2-C10 alkenylcarbonyloxy, C3-C10 cycloalkylcarbonyloxy, C6-C20 arylcarbonyloxy, haloC1-C10 alkylcarbonyloxy, C1-C10 alkylcarbonylamine, and haloC1-C10 alkylcarbonylamine, which is preferred in terms of more efficiently carrying out a ligand dissociation reaction upon exposure.

[0054] In a preferred embodiment, the organic ligand may be any one or more selected from the group consisting of formic acid, C1-C10 alkyl carboxylate, halo C1-C10 alkyl carboxylate, and halo C1-C10 alkylcarbonyloxy. Specifically, the organic ligand may be any one or more selected from the group consisting of C1-C5 alkyl carboxylate, halo C1-C5 alkyl carboxylate, and halo C1-C5 alkylcarbonyloxy. When the tin compound contains such an organic ligand, the tin atom bonds with an oxygen atom present in the organic ligand, making the tin compound more thermodynamically stable.

[0055] For example, the tin compound may be represented by the following chemical formulas 1 to 4.

[0056] [Chemical formula 1] JPEG0007745295000005.jpg37170

[0057] [Chemical formula 2] JPEG0007745295000006.jpg37170

[0058] [Chemical formula 3] JPEG0007745295000007.jpg23170

[0059] [Chemical formula 4] JPEG0007745295000008.jpg14170

[0060] (In the above chemical formulas 1 to 4, R1 to R7 are each independently hydrogen, C1-C10 alkyl, or haloC1-C10 alkyl.

[0061] For example, R1 to R7 may be, independently of each other, hydrogen, C1-C5 alkyl, or haloC1-C5 alkyl.

[0062] For example, R1 to R4 may be each independently C1-C5 alkyl or haloC1-C5 alkyl, and R5 to R7 may be each independently hydrogen, C1-C5 alkyl, or haloC1-C5 alkyl.

[0063] For example, R1 and R2 may be the same as each other and be C1-C5 alkyl or haloC1-C5 alkyl, R3 and R4 may be the same as each other and be C1-C5 alkyl or haloC1-C5 alkyl, and R5 to R7 may be each independently be hydrogen, C1-C5 alkyl, or haloC1-C5 alkyl.

[0064] For example, R1 and R2 may be the same as each other and represent C1-C3 alkyl or haloC1-C3 alkyl, R3 and R4 may be the same as each other and represent C1-C3 alkyl or haloC1-C3 alkyl, and R5 to R7 may be each independently represent hydrogen, C1-C3 alkyl, or haloC1-C3 alkyl.

[0065] The present disclosure also provides a photoresist composition comprising the above-described tin compound.

[0066] In one embodiment, the photoresist composition is an inorganic resist for extreme ultraviolet (EUV) and / or electron beam lithography. Upon irradiation with extreme ultraviolet (EUV) or an electron beam, chemical symmetry is developed through an additive reaction between inorganic components, allowing pattern formation in an optional development step.

[0067] The tin compound according to the present disclosure has a structure in which a central skeleton containing a tin-oxygen double bond is bonded to an oxygen atom of an organic ligand, and the organic ligand dissociates upon exposure. Due to the volume occupied by the organic ligand, the molecules exist within close distance from each other and can be polymerized with each other by an addition reaction.

[0068] The photoresist composition according to one embodiment may be an extreme ultraviolet (EUV) photoresist composition.

[0069] The photoresist composition according to one embodiment has excellent extreme ultraviolet light sensitivity and corrosion resistance, so that a photoresist pattern using the composition can be formed with a thin thickness even in an ultra-fine pattern, and also can form a high-quality photoresist pattern with excellent resolution and sensitivity.

[0070] In one embodiment, the photoresist composition according to the present disclosure may contain a tin compound and a solvent. Any solvent can be used as long as it dissolves the tin compound according to one embodiment. For example, the solvent may be one or more selected from the group consisting of water, methanol, acetic acid, chlorobenzene, chloroform, ethyl lactate, and tetrahydrofuran.

[0071] In one embodiment, the photoresist composition may contain 0.1 to 50 parts by weight of the tin compound as described above, based on 100 parts by weight of the total weight of the photoresist composition. Specifically, the tin compound may be contained in an amount of 0.1 to 30 parts by weight, more specifically 0.5 to 10 parts by weight, and even more specifically 1 to 5 parts by weight, based on 100 parts by weight of the photoresist composition. When the content of the tin compound satisfies the above range, a photoresist pattern with even better resolution and sensitivity can be formed, which is preferable.

[0072] The present disclosure also provides a method for forming a photoresist pattern, which includes a step in which, upon exposure, the organic ligands of the organometallic compound dissociate and an addition reaction between metal molecules occurs.

[0073] According to one embodiment of the method for forming a photoresist pattern, it is possible to prevent the conventional problem of reduced pattern reproducibility due to external environments such as moisture and carbon dioxide, and also to form a high-quality photoresist pattern without including a step of reacting with gas molecules during the process, which is very useful industrially.

[0074] For example, the organometallic compound may contain a metal having excellent photosensitivity as a central metal, specifically, an organotin compound. Examples of applicable organic ligands are as described above.

[0075] The method for forming a photoresist pattern according to the present disclosure includes a step of performing an addition reaction between metal molecules during exposure, thereby preventing the conventional problem of reduced pattern reproducibility due to external environments such as moisture and carbon dioxide, and thus enabling the formation of high-quality photoresist patterns in large-area processes with excellent reproducibility and process stability.

[0076] The present disclosure also provides a method for forming a photoresist pattern, comprising the steps of: (a) applying a photoresist composition containing the organometallic compound described above to a substrate to form a thin film; (b) exposing the thin film to light; and (c) developing the exposed thin film using a developer solution.

[0077] In one embodiment, the organometallic compound may include a central skeleton containing a tin-oxygen double bond and organic ligands bonded to the central skeleton.

[0078] For example, the central skeleton may be tin dioxide (O=Sn=O) or tin monoxide (O=Sn). According to the method for forming a photoresist pattern disclosed herein, upon exposure, the organic ligands of the organometallic compound dissociate, and the central skeleton molecules are within close proximity due to the volume previously occupied by the organic ligands, allowing them to polymerize with each other through an addition reaction. Schematic diagrams of this mechanism are shown in Figures 1 and 2.

[0079] In the method for forming a photoresist pattern according to one embodiment, the photoresist composition in step (a) may be applied to a substrate by any method known in the art, including, but not limited to, spin coating, dipping, roller coating, bar coating, spray coating, inkjet printing, and screen printing.

[0080] For example, the photoresist composition can be applied to a substrate by spin coating, where the desired thickness of the photoresist film can be adjusted based on the spinner speed and coating time. For example, spin coating can be performed at a speed of 100 rpm to 5000 rpm, specifically 2000 rpm to 4000 rpm, for 1 second to 60 seconds, specifically 20 seconds to 40 seconds, but is not limited thereto.

[0081] In one embodiment, step (b) is a step of exposing the thin film formed in step (a), and the exposure may be performed by any one selected from an electron beam (E-beam), extreme ultraviolet (EUV), I-line, krypton fluoride (KrF) laser, argon fluoride (ArF) laser, deep ultraviolet (DUV), vacuum ultraviolet (VUV), X-ray, and ion beam, preferably extreme ultraviolet or electron beam, but not necessarily limited thereto.

[0082] In one embodiment, the method may further include a step of heating the thin film formed in step (a) after step (a) and before step (b). The step of heating the thin film is a PAB (Postapply Bake) process, which may be performed at 50 to 300°C, specifically at 100 to 200°C or 110 to 180°C, for 0.5 to 10 minutes or 0.5 to 5 minutes, thereby removing the solvent contained in the photoresist composition and improving the adhesion between the thin film and the substrate.

[0083] In one embodiment, the thickness of the photoresist thin film formed on the substrate may be 1 to 100 nm, or 5 to 50 nm, specifically 5 to 30 nm, where the thickness may be measured after applying the photoresist composition to the substrate and then performing the PAB process described above.

[0084] The substrate onto which the photoresist composition is applied may include one or more conductive layers selected from aluminum, copper, molybdenum, titanium, tungsten, alloys of these metals, nitrides of these metals, or silicides of these metals, one or more dielectric layers selected from silicon oxide, silicon nitride, silicon oxynitride, and metal oxide, a semiconductor layer such as single crystal silicon, or a combination thereof, located on a lower base substrate. Here, the lower base substrate may be in the form of a wafer or film, and may be a laminate in which semiconductors, ceramics, metals, polymers, or two or more materials selected from these are stacked in layers.

[0085] For example, the lower base substrate may be a semiconductor substrate, and non-limiting examples of the semiconductor substrate may include a Group IV semiconductor including silicon (Si), germanium (Ge), or silicon germanium (SiGe), a Group III-V semiconductor including gallium arsenide (GaAs), indium indium (InP), or gallium indium (GaP), a Group II-VI semiconductor including cadmium sulfide (CdS) or zinc telluride (ZnTe), a Group IV-VI semiconductor including lead sulfide (PbS), or a stacked body in which two or more materials selected from the above are stacked in layers. Here, the semiconductor substrate may be in the form of a wafer or a film, and may be a semiconductor, ceramic, metal, polymer, or a stacked body in which two or more materials selected from the above are stacked in layers.

[0086] In one embodiment, the method may further include a step of heating the exposed thin film after step (b). Specifically, the step of heating the exposed thin film is a PEB (postexposure bake) process, which may be performed at 50 to 300°C, specifically at a temperature of 100 to 200°C or 100 to 150°C for 1 to 15 minutes or 1 to 5 minutes. This can further increase the difference in developer solubility between the exposed and unexposed regions.

[0087] In one embodiment, a UV bake step of baking the photoresist thin film by ultraviolet (UV) irradiation may be further included before and / or after step (b), which can improve the quality of the inorganic resist pattern, such as dose-to-size (DtS), line edge roughness (LER), and line width (half-pitch, HP). For example, the UV bake step may use a UV lamp, an i-line light source, a KrF laser light source, an ArF laser light source, or the like, but is not limited thereto.

[0088] In one embodiment, after step (c), a hard bake step of baking the photoresist thin film may be further included, which can further improve the quality of the inorganic resist pattern, such as dose-to-size (DtS), edge roughness (LER), and line width (half-pitch, HP). For example, the hard bake step may be performed at a temperature of 100°C to 200°C, specifically 110°C to 180°C, for 0.5 to 10 minutes, specifically 0.5 to 5 minutes, but is not necessarily limited thereto, and the process conditions may be appropriately changed depending on the solvent used.

[0089] The light source may be a KrF or ArF laser light source, but is not limited to this.

[0090] In one embodiment, the photoresist pattern may be a positive type that becomes soluble in a developer upon exposure to light used in the exposure step, or a negative type that becomes insoluble in a developer, specifically a negative type. That is, depending on the solubility of the thin film in a developer, the pattern formed by the photoresist pattern forming method may be a positive type or a negative type pattern, specifically a negative type pattern.

[0091] In one embodiment, step (c) involves developing the exposed thin film using a developer solution. Specifically, the developer solution may be any type known in the art, and may include, for example, a C2-10 alkene or a quaternary ammonium salt. A specific example of the C2-10 alkene is hexene. A specific example of the quaternary ammonium salt is tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), tetrapropylammonium hydroxide (TPAH), tetraethylammonium hydroxide (TEAH), or a mixture thereof. For example, the developer may include, but is not limited to, 1 to 30% by weight, specifically 1 to 5% by weight, of a quaternary ammonium salt.

[0092] The present invention also provides a semiconductor device including a photoresist pattern formed by the above-described method for forming a photoresist pattern. The semiconductor device includes a photoresist pattern formed with excellent resolution and sensitivity by the above-described method, thereby realizing a semiconductor device of higher quality.

[0093] Examples and experimental examples are specifically illustrated below. However, the examples and experimental examples described below are only partial examples, and the technology described in this specification is not limited thereto.

[0094] [Example 1] Production of tin compound 1 JPEG0007745295000009.jpg37170

[0095] 0.304 g of tin oxide powder (purchased from QURES Co., Ltd.) was placed in a round-bottom flask, followed by 16 ml of methanol and 24 ml of acetic acid. After stirring at room temperature for 30 minutes, the mixture was heated to 70°C and stirred for 15 hours. The solvent was then removed using a vacuum pump to obtain a yellow solid tin compound 1 (acetic acid-stabilized tin dioxide).

[0096] To analyze the structure of the obtained tin compound, a MolDietof mass spectrometer (MALDI-TOF MS) was used. Tin compound 1 was dissolved in methanol at 1 wt% to prepare a solution, which was then filtered through a 5 ml PTFE syringe filter and used for analysis. The analysis results are shown in Figure 3. The molecular formula of the peak corresponding to (a) in Figure 3 was estimated by isotope distribution simulation calculations and shown in Figure 4, and the result corresponding to (b) is shown in Figure 5. Referring to Figure 4, the peak distributed at around 272.929 Da was [SnO2(CH3COOH)2+H] + When the molecular formula was substituted, the isotope distribution graph was confirmed to match. Also, referring to Figure 5, the distributed mass near 294.944 Da is [SnO2(CH3COOH)2+Na] + When the molecular formula was substituted, it was confirmed that the isotope distribution graph matched. The solid line shows the MALDI-TOF analysis results, and the dotted line shows the data obtained by simulation calculation.

[0097] The obtained tin compound was also analyzed in a solid powder state by X-ray photoelectron spectroscopy (XPS), and the results are shown in Figure 6. Referring to Figure 6, peaks were observed at 486.7 eV for Sn3d3 and 495.1 eV for Sn3d5, confirming that the tin atom in the obtained tin compound 1 has a tetravalent oxidation state.

[0098] [Example 2] Preparation of tin compound 2 JPEG0007745295000010.jpg38170

[0099] Tin Compound 2 (acetic acid-stabilized tin monoxide) was obtained in the same manner as in Example 1, except that 0.608 g of tin oxide powder was used, and the mixture was stirred at room temperature for 30 minutes, and then stirred with heating for 1 hour.

[0100] To analyze the structure of the obtained tin compound, FD-MS (Field Desorption-Mass Spectrometry) analysis was performed. Tin compound 2 was dissolved in acetic acid at 2 wt% to prepare a solution, which was then filtered through a 5 ml PTFE syringe filter and used for analysis. The analysis results are shown in Figure 7, and the molecular formula estimated by isotope distribution simulation calculation is shown in Figure 8. Referring to Figure 8, [SnOLi] was found with a distributed mass of approximately 142.91 Da. + When the molecular formula was substituted, the isotope distribution graph was confirmed to match. Li is expected to be derived from the promoter LiI used in acetic acid synthesis. The black solid line is the FD-MS analysis result, and the red dotted line is the data obtained by simulation calculation.

[0101] The obtained tin compound was analyzed in a solid powder state by FT-IR spectroscopy, and the results are shown in Figure 9. -1 The peak confirmed the presence of C=O, which confirmed that acetic acid was not completely removed and was still present in the obtained tin compound 2.

[0102] [Example 3] Preparation of tin compounds 3-1 and 3-2 JPEG0007745295000011.jpg31170

[0103] Tin compounds 3-1 and 3-2 were obtained in the same manner as in Example 2, except that trifluoroacetic acid was used instead of acetic acid.

[0104] To analyze the structures of the obtained tin compounds, a MolDietof mass spectrometer (MALDI-TOF MS) was used. Tin compounds 3-1 and 3-2 were dissolved in methanol at 1 wt% to prepare a solution, which was then filtered through a 5 ml PTFE syringe filter and used for analysis. The analysis results are shown in Figure 10. The molecular formulas estimated by isotope distribution simulation calculations for the peak corresponding to (a) in Figure 10 are shown in Figure 11, and the results corresponding to (b) are shown in Figure 12.

[0105] Referring to Figure 11, [SnO(CF3COOH)+Na] is distributed at a mass near 271.93 Da. + When the molecular formula was substituted, it was confirmed that the isotope distribution graph matched, and it was confirmed that a compound corresponding to the tin compound 3-1 was produced.

[0106] 12, when the molecular formula of SnO(CFCOO)(HCOO) was substituted for the distributed mass near 293.98 Da, the isotope distribution graph matched, confirming that a compound corresponding to tin compound 3-2 was produced. The solid line represents the MALDI-TOF analysis results, and the dotted line represents data obtained by simulation.

[0107] [Examples 4 to 8] Preparation of photoresist compositions Photoresist compositions were prepared by dissolving the tin compounds obtained in Examples 1 to 3 in solvents. The contents of the tin compounds and the types of solvents are shown in Table 1 below.

[0108] [Table 1]

[0109] [Example 9] Formation of photoresist pattern using extreme ultraviolet (EUV) A p-Si silicon wafer on which a 100 nm thick thermal oxide film (SiO2) had been deposited was cut into 1.5 cm x 1.5 cm pieces and then cleaned by sonication in acetone for 20 minutes. The photoresist composition prepared in Example 4 was applied to the wafer and spin-coated (1500 rpm, 30 s) to form a thin film, which was then heated at 90°C for 1 minute to remove the solvent. Extreme ultraviolet (EUV) light was applied to the thin film at 30-130 mJ / cm. 2 The exposure dose was 130 mJ / cm. The film was then heated at 90°C for 1 minute to perform PEB, immersed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) developer, and developed for 10 seconds to obtain a pattern. The results were observed using a CD-SEM (Critical Dimension Scanning Electron Microscope) and were 130 mJ / cm. 2 The pattern irradiated with an exposure dose of 120 mJ / cm is shown in Figure 13. 2 The pattern irradiated with an exposure dose of 110 mJ / cm is shown in Figure 14. 2 The pattern irradiated with an exposure dose of 100 mJ / cm is shown in Figure 15. 2 The pattern irradiated with an exposure dose of 90 mJ / cm is shown in Figure 16. 2 The pattern irradiated with an exposure dose of 80 mJ / cm is shown in Figure 17. 2 The pattern irradiated with an exposure dose of 70 mJ / cm is shown in Figure 18. 2 The pattern irradiated with an exposure dose of 60 mJ / cm is shown in Figure 19. 2 The pattern irradiated with an exposure dose of 50 mJ / cm is shown in Figure 20. 2 The pattern irradiated with an exposure dose of 40 mJ / cm is shown in Figure 21. 2 The pattern irradiated with an exposure dose of 1000 μm is shown in Figure 22. This confirms that the photoresist composition containing the tin compound according to the present disclosure can stably form a high-quality ultrafine pattern even with a low exposure dose.

[0110] [Example 10] Formation of photoresist pattern using electron beam A p-Si silicon wafer on which a 100 nm thick thermal oxide film (SiO2) had been deposited was cut into 1.5 cm x 1.5 cm pieces and then cleaned by sonication in acetone for 20 minutes. The photoresist composition prepared in Example 5 was applied to the wafer and spin-coated (3000 rpm, 30 s) to form a thin film, which was then heated at 50°C for 1 minute to remove the solvent. The thin film was then subjected to irradiation with an electron beam at 200-5000 μC / cm. 2 The substrate was then immersed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) developer for 10 seconds to obtain a pattern. The results were observed with an atomic force microscope (AFM) and a field emission scanning electron microscope (FE-SEM), and are shown in Figure 23. After development with an atomic force microscope (AFM), the remaining thickness of the exposed and unexposed regions was analyzed, and a 500 μC / cm 2 It was confirmed that an ultrafine pattern was stably formed at this exposure dose.

[0111] [Experimental Example 1] Measurement of ND (Non-dissolution) temperature A p-Si silicon wafer with a 100 nm thick thermal oxide (SiO2) deposited on it was cut into 1.5 cm x 1.5 cm pieces and cleaned by sonication in acetone for 20 minutes. The photoresist compositions prepared in Examples 4 to 8 were applied to the wafer and spin-coated (1500-3000 rpm, 30 s) to form thin films. The temperature was then monitored to determine whether the composition dissolved in the developer. A 2.38 wt% solution of tetramethylammonium hydroxide (TMAH) was used as the developer, and the temperature at which the composition no longer dissolved in the developer upon heating was defined as the nondissolution temperature (ND). The analytical results are shown in Table 2 below. This confirms the maximum applicable temperature for the PAB and PEB processes of the photoresist composition according to the present disclosure. It can be seen that the photoresist composition according to the present disclosure has excellent thermal stability, does not collapse, and can form high-quality photoresist patterns even at high temperatures.

[0112] [Table 2]

[0113] [Experimental Example 2] Measurement of electron beam sensitivity The photoresist compositions prepared in Examples 5 to 7 were used to measure the electron beam sensitivity.

[0114] A p-Si silicon wafer on which a 100 nm thick thermal oxide film (SiO2) was deposited was cut into 1.5 cm x 1.5 cm pieces and then cleaned by sonication in acetone for 20 minutes. The photoresist compositions prepared in Examples 5 to 7 were applied to the wafer and spin-coated (3000 rpm, 30 s) to form thin films, followed by a PAB process. The thin films were then irradiated with an electron beam at 1 to 1000 μC / cm. 2 The film was then immersed in a 2.38 wt % tetramethylammonium hydroxide (TMAH) developer and developed for 10 seconds to obtain a pattern. The composition and process conditions used are shown in Table 3 below. The thickness of the obtained pattern was measured using an atomic force microscope (AFM), and the results are shown in Figures 24 to 26. 50 means the exposure dose when the remaining thickness of the thin film is half, and D 100 means the exposure dose at which the remaining thickness of the thin film is at its maximum. The thickness of the thin film was calculated as the average thickness of the thin film remaining after exposure at the exposure dose.

[0115] [Table 3]

[0116] 24 is a graph showing the thickness of the thin film remaining after development of the pattern obtained using the photoresist composition of Example 5. The measured value was D0 4.5 μC / cm 2 , D 50 6.0μC / cm 2 , D 100 8.25μC / cm 2 The contrast γ, which is the gradient of the graph of the film thickness as a function of the exposure dose, was found to be 3.79.

[0117] 25 is a graph showing the thickness of the thin film remaining after development of the pattern obtained using the photoresist composition of Example 6. The measured values ​​are D 50 22.88μC / cm 2 The contrast γ, which is the gradient of the graph of the film thickness as a function of the exposure dose, was found to be 2.30.

[0118] 26 is a graph showing the thickness of the thin film remaining after development of the pattern obtained using the photoresist composition of Example 7. The measured value was D082.64 μC / cm 2 , D 50 100μC / cm 2 , D 100 121μC / cm 2 The contrast γ, which is the gradient of the graph of the film thickness as a function of the exposure dose, was found to be 6.04.

[0119] As can be seen from the above, a photoresist composition containing a tin compound according to an embodiment of the present disclosure can simultaneously achieve excellent photosensitivity and corrosion resistance, and can be used to manufacture high-quality semiconductor devices. Furthermore, during exposure, the organic ligands of the tin compound dissociate and undergo an addition reaction between tin molecules to polymerize with each other, thereby generating a pattern in the development process. This prevents the conventional problem of reduced pattern reproducibility due to external environments such as moisture and carbon dioxide.

[0120] As described above, in this specification, the present disclosure has been described using specific matters and limited examples, but these are provided to facilitate a more general understanding of the present disclosure. The present disclosure is not limited to the above examples, and various modifications and variations can be made from such descriptions by those having ordinary knowledge in the field to which the present disclosure pertains.

Claims

1. a central skeleton containing a tin-oxygen double bond; an organic ligand bonded to the central skeleton, The organic ligand is at least one selected from the group consisting of formic acid, C1-C10 alkyl carboxylate, C2-C10 alkenyl carboxylate, C3-C10 cycloalkyl carboxylate, C6-C20 aryl carboxylate, halo C1-C10 alkyl carboxylate, C1-C10 alkylcarbonyloxy, C2-C10 alkenylcarbonyloxy, C3-C10 cycloalkylcarbonyloxy, C6-C20 arylcarbonyloxy, halo C1-C10 alkylcarbonyloxy, C1-C10 alkylcarbonylamine, and halo C1-C10 alkylcarbonylamine.

2. 2. The tin compound according to claim 1, wherein the central skeleton is tin dioxide (O=Sn=O) or tin monoxide (O=Sn).

3. The tin compound according to claim 1, represented by any one of the following chemical formulas 1 to 4: [Chemical formula 1] 【Chemical 1】 [Chemical formula 2] 【Chemistry 2】 [Chemical formula 3] 【Chemistry 3】 [Chemical formula 4] 【Chemistry 4】 In the above chemical formulas 1 to 4, R １ ~R ７ are each independently hydrogen, C1-C10 alkyl or haloC1-C10 alkyl.

4. R １ ~R ４ are, independently of each other, C1-C5 alkyl or haloC1-C5 alkyl; R ５ ~R ７ are each independently hydrogen, C1-C5 alkyl or haloC1-C5 alkyl.

5. A photoresist composition comprising the tin compound according to any one of claims 1 to 4.

6. The photoresist composition of claim 5, which forms a pattern by an optional development step after irradiation with extreme ultraviolet (EUV) or electron beam.

7. The photoresist composition of claim 5 which is an extreme ultraviolet (EUV) photoresist.

8. 6. The photoresist composition according to claim 5, wherein the total content of the tin compounds is 0.1 to 50 parts by weight based on 100 parts by weight of the photoresist composition.

9. 6. The photoresist composition according to claim 5, wherein the total content of the tin compounds is 0.1 to 10 parts by weight based on 100 parts by weight of the photoresist composition.

10. A method for forming a photoresist pattern, comprising the steps of: upon exposure, dissociating an organic ligand of an organometallic compound and causing a polymerization reaction between the organometallic compounds; The organometallic compound comprises a central skeleton including a tin-oxygen double bond and an organic ligand bonded to the central skeleton; The method for forming a photoresist pattern as described above, wherein the organic ligand is at least one selected from the group consisting of formic acid, C1-C10 alkyl carboxylate, C2-C10 alkenyl carboxylate, C3-C10 cycloalkyl carboxylate, C6-C20 aryl carboxylate, halo C1-C10 alkyl carboxylate, C1-C10 alkylcarbonyloxy, C2-C10 alkenylcarbonyloxy, C3-C10 cycloalkylcarbonyloxy, C6-C20 arylcarbonyloxy, halo C1-C10 alkylcarbonyloxy, C1-C10 alkylcarbonylamine, and halo C1-C10 alkylcarbonylamine.

11. (a) applying a photoresist composition containing the organometallic compound to a substrate to form a thin film; (b) exposing the thin film to light; 11. The method for forming a photoresist pattern according to claim 10, further comprising: (c) developing the exposed thin film with a developer solution.

12. 11. The method of forming a photoresist pattern according to claim 10, wherein the central skeleton is tin dioxide (O=Sn=O) or tin monoxide (O=Sn).

13. 12. The method of claim 11, wherein the exposure in step (b) is performed using any one selected from the group consisting of an electron beam (E-beam), extreme ultraviolet (EUV), I-line, krypton fluoride (KrF) laser, argon fluoride (ArF) laser, deep ultraviolet (DUV), vacuum ultraviolet (VUV), X-ray, and ion beam.

14. 12. The method for forming a photoresist pattern according to claim 11, further comprising the step of heating the thin film formed in the step (a) before the step (b).

15. 12. The method for forming a photoresist pattern according to claim 11, further comprising the step of heating the exposed thin film after the step (b).

16. A semiconductor device comprising a photoresist pattern formed by the photoresist composition of claim 5.

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