Resist compounds and underlayer compounds for photolithography and multilayer structures

Abstract

Provided are resist compounds and primer compounds for photolithography, multilayer structures, and methods for manufacturing semiconductor devices. The resist compounds and the primer compounds can improve resolution and sensitivity of a resist pattern and inhibit collapse of the resist pattern. The primer compounds include a cellulose structure having at least one hydroxyl group (-OH) and at least one vinylsilyl group. The resist compounds include an alkylated metal oxide nanocluster having a counter anion.

Description

[0001] This application claims priority to Korean Patent Application No. 10-2022-0060058, filed on May 17, 2022, and Korean Patent Application No. 10-2022-0186178, filed on December 27, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This disclosure relates to resist compounds and padding compounds for photolithography, multilayer structures formed using the resist compounds and padding compounds, and methods for manufacturing semiconductor devices using the resist compounds and padding compounds. Background Technology

[0003] Photolithography can include an exposure process and a development process. The exposure process can include exposing a resist layer to light of a specific wavelength to cause a change in the chemical structure of the resist layer. The development process can include selectively removing either the exposed or unexposed portions of the resist layer by utilizing the difference in solubility between the exposed and unexposed portions.

[0004] Recently, with the high integration and miniaturization of semiconductor devices, the linewidth of patterns in semiconductor devices has been reduced. In order to form tiny patterns, various studies have been conducted to improve the resolution and sensitivity of resist patterns formed by photolithography and to suppress resist pattern collapse. Summary of the Invention

[0005] The objective of this disclosure is to provide a resist compound and a pad compound that can improve the resolution and sensitivity of resist patterns and suppress resist pattern collapse, a multilayer structure formed using the resist compound and the pad compound, and a method for manufacturing a semiconductor device using the resist compound and the pad compound.

[0006] The tasks addressed by this disclosure are not limited to those described above, and other tasks not mentioned will be clearly understood by those skilled in the art from the following description.

[0007] According to an embodiment of the inventive concept, a padding compound for photolithography may include the structure of Formula 1.

[0008] [Formula 1]

[0009]

[0010] In Equation 1, R1, R2 and R3 are each independently hydrogen, deuterium or functional groups represented by Equation 2, Equation 3 or Equation 4, and "n" is an integer from 2 to 10000.

[0011] [Equation 2]

[0012]

[0013] [Formula 3]

[0014]

[0015] [Formula 4]

[0016]

[0017] In Equations 2 and 4, "m" is an integer from 1 to 20.

[0018] In Formulas 3 and 4, R4, R5, R6, R7 and R8 are each independently hydrogen, deuterium or an alkyl group with one to three carbon atoms.

[0019] In Equations 2 to 4, * represents the part that combines with oxygen in Equation 1.

[0020] The photoresist compound for photolithography according to the inventive concept may include alkylated metal oxide nanoclusters having counter anions. The alkylated metal oxide nanoclusters may include a core structure comprising a metal oxide and an alkyl group of 1 to 20 carbon atoms bonded to the metal element of the core structure. The counter anion may be an alkyl carboxylic acid anion of 2 to 20 carbon atoms, an alkyl ether alkyl carboxylic acid anion of 3 to 20 carbon atoms, an alkyl ether alkyl carboxylic acid anion of 4 to 20 carbon atoms, a fluoroalkyl carboxylic acid anion of 2 to 20 carbon atoms, a fluoroalkyl ether fluoroalkyl carboxylic acid anion of 3 to 20 carbon atoms, or a fluoroalkyl ether fluoroalkyl carboxylic acid anion of 4 to 20 carbon atoms.

[0021] The multilayer structure according to the inventive concept may include a lower layer, a pad layer on the lower layer, and a photoresist layer on the pad layer. The pad layer may include a cellulose structure having at least one hydroxyl (-OH) group and at least one vinylsilyl group. The photoresist layer may include alkylated metal oxide nanoclusters having counter-anions. The alkylated metal oxide nanoclusters may include a core structure comprising a metal oxide and an alkyl group of 1 to 20 carbon atoms bonded to the metal element of the core structure.

[0022] A method for manufacturing a semiconductor device according to the inventive concept may include: forming a pad layer on a lower layer; and forming a photoresist layer on the pad layer. The step of forming the photoresist layer may include applying a photoresist compound to the pad layer using a hydrophobic solvent or an aromatic solvent. The pad layer may include a pad layer compound having hydrophilic properties. The pad layer compound may include a cellulose structure having at least one hydroxyl (-OH) group and at least one vinylsilyl group. Attached Figure Description

[0023] The accompanying drawings are included to provide a further understanding of the inventive concept, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the inventive concept and, together with the description, serve to explain the principles of the inventive concept. In the drawings:

[0024] Figure 1 This is a graph showing the nuclear magnetic resonance spectrum results of the cushioning compound prepared according to Synthesis Example 1;

[0025] Figure 2 This is a graph showing the Fourier transform infrared (FT-IR) spectrum of the pad film formed according to synthesis example 2;

[0026] Figure 3 and Figure 4 This is a graph showing the evaluation results of the solubility of the cushioning compounds according to Experimental Example 1 and Experimental Example 2;

[0027] Figures 5 to 8 This is a cross-sectional view illustrating a method for manufacturing a semiconductor device according to an embodiment of the inventive concept;

[0028] Figure 9 Atomic force microscopy images showing the results of surface roughness measurements of the pad and photoresist film formed according to Experimental Example 3 are shown.

[0029] Figure 10 This is a graph showing the evaluation results of the solubility change of the photoresist film according to Experimental Example 4;

[0030] Figure 11 A scanning electron microscope image of the photoresist pattern formed according to Experimental Example 5 is shown; and

[0031] Figure 12 This is a graph showing the evaluation results of the solubility change of the photoresist film according to Experimental Example 6. Detailed Implementation

[0032] To fully understand the structure and effects of the inventive concept, preferred embodiments will be explained with reference to the accompanying drawings. However, the inventive concept can be implemented in various forms with various modifications and should not be construed as limited to the embodiments set forth herein. Embodiments are provided so that the disclosure of the inventive concept is complete through explanation of the embodiments, and to fully inform those skilled in the art to which the inventive concept pertains of the scope of the inventive concept.

[0033] The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the inventive concept. In this disclosure, the singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will also be understood that, when used in this specification, the terms “comprising” and / or “including” indicate the presence of the stated elements, but do not exclude the presence or addition of one or more other elements.

[0034] In this description, unless otherwise indicated, alkyl groups include monovalent saturated hydrocarbon groups that are straight-chain, branched, or cyclic.

[0035] In the description, unless otherwise defined, the absence of chemical bonds at locations where chemical bonds are required can indicate that hydrogen atoms are bonded.

[0036] In the following, embodiments of the inventive concept will be explained in detail with reference to the accompanying drawings. The same reference numerals are used for the same constituent elements in the drawings, and repeated descriptions thereof will be omitted.

[0037] The underlayer compound according to embodiments of the inventive concept will be explained.

[0038] The padding compound according to embodiments of the inventive concept can be used to manufacture semiconductor devices and can be used in photolithography processes for manufacturing semiconductor devices. The padding compound can be used, for example, in extreme ultraviolet (EUV) lithography or electron beam lithography processes. Extreme ultraviolet (EUV) can refer to ultraviolet light having a wavelength of about 10 nm to about 124 nm, more specifically, ultraviolet light having a wavelength of about 13.0 nm to about 13.9 nm, and more specifically, ultraviolet light having a wavelength of about 13.4 nm to about 13.6 nm.

[0039] The padding compound may comprise a cellulose structure having at least one hydroxyl (-OH) group and at least one vinylsilyl group. The padding compound may comprise a structure of Formula 1.

[0040] [Formula 1]

[0041]

[0042] In Equation 1, R1, R2, and R3 are each independently hydrogen, deuterium, or functional groups represented by Equation 2, Equation 3, or Equation 4. In Equation 1, "n" is an integer from 2 to 10000.

[0043] [Equation 2]

[0044]

[0045] [Formula 3]

[0046]

[0047] [Formula 4]

[0048]

[0049] In Equations 2 and 4, "m" is an integer from 1 to 20.

[0050] In Formulas 3 and 4, R4, R5, R6, R7 and R8 are each independently hydrogen, deuterium or an alkyl group with one to three carbon atoms.

[0051] In Equations 2 to 4, * represents the part that combines with oxygen in Equation 1.

[0052] Each of Formulas 3 and 4 may include vinylsilyl groups and their derivatives. For example, Formula 3 may include functional groups represented by Formula 3-1, and Formula 4 may include functional groups represented by Formula 4-1.

[0053] [Equation 3-1]

[0054]

[0055] [Equation 4-1]

[0056]

[0057] In Equations 3-1 and 4-1, * is the part that combines with oxygen in Equation 1, and “m” is an integer from 1 to 20.

[0058] In Formula 1, at least one of R1, R2, and R3 can be a functional group represented by Formula 3 or Formula 4. Therefore, the padding compound can include vinylsilyl groups and their derivatives. The vinylsilyl group of the padding compound can form chemical bonds with free radicals generated by the resist compound, which will be explained later.

[0059] In Formula 1, the other of R1, R2, and R3 can be hydrogen, deuterium, or a functional group represented by Formula 2. Therefore, the padding compound can include hydroxyl groups (-OH) and can be hydrophilic.

[0060] According to some embodiments, the cushioning compound may include a cross-linked structure of a substance represented by Formula 1, cross-linked using tetra(methoxymethyl)glycourea (TMMGU) as a curing agent. In embodiments, the cushioning compound may include a structure of Formula 5. Formula 5 may be a cross-linked structure of a substance represented by Formula 1, cross-linked using tetra(methoxymethyl)glycourea (TMMGU) as a curing agent. Formula 5 may be a structure formed by reacting the hydroxyl group (-OH) of Formula 1 with the -CH3 group of TMMGU.

[0061] [Formula 5]

[0062]

[0063] In Formula 5, A1, A2, A3 and A4 may each independently include a cellulose structure having at least one hydroxyl group (-OH) and at least one vinyl silyl group.

[0064] In Equation 5, A1, A2, A3 and A4 can each be independently represented by Equation 6, Equation 7, Equation 8, Equation 9, Equation 10 or Equation 11.

[0065] [Formula 6]

[0066]

[0067] [Formula 7]

[0068]

[0069] [Formula 8]

[0070]

[0071] [Formula 9]

[0072]

[0073] [Formula 10]

[0074]

[0075] [Equation 11]

[0076]

[0077] In Equations 6 to 11, R1, R2, and R3 are each independently hydrogen, deuterium, or a functional group represented by Equation 2, 3, or 4. “n” is an integer from 2 to 10000, and “m1” is an integer from 0 to 19. A value of 0 for “m1” indicates the formation of a single bond between oxygen and carbon. In Equations 6 to 11, * represents the portion bonded to carbon in Equation 5.

[0078] In Formulas 6 to 11, at least one of R1, R2, and R3 can be a functional group represented by Formula 3 or Formula 4. Therefore, the padding compound can include vinylsilyl groups and their derivatives. The vinylsilyl group of the padding compound can form a chemical bond with a free radical generated by the resist compound, which will be explained later. In Formulas 6 to 11, the other of R1, R2, and R3 can be hydrogen, deuterium, or a functional group represented by Formula 2. Therefore, the padding compound can include a hydroxyl group (-OH) and can be hydrophilic.

[0079] The synthesis of the cushioning compound of Formula 1 can be carried out according to reaction 1.

[0080] [Reaction 1]

[0081]

[0082] In reaction 1, the initial substances R9 and R... 10 and R 11 It can be hydrogen, deuterium, or a functional group represented by Formula 2. At least one hydroxyl group (-OH) of the starting material can be substituted with a vinylsilyl group, thus, a cushioning compound of Formula 1 can be prepared. In reaction 1, "n" is an integer from 2 to 10000.

[0083] [Synthetic Example 1] Synthesis of the cushioning compound of Formula 1 (Reaction 1)

[0084] 100cm 3 Hydroxypropyl cellulose (HPC, 1 g), saccharin (2.2 mg), and 1,4-dioxane (20 cm) were injected into a sealed tube. 3 The solution obtained by dissolving HPC at approximately 100°C was then cooled to room temperature. The sealed tube was opened, and 1,3-divinyltetramethyldisilazane (DVS, 0.44 g) was injected. The reaction was then carried out at approximately 120°C for approximately 12 hours. The resulting reaction solution was cooled to room temperature. Tetrahydrofuran (THF, 20 cm⁻¹) was then added. 3 The product is injected into the reaction solution for dilution, and the diluted reaction solution is added dropwise to hexane to form a precipitate. The resulting product is filtered and dried to obtain the final product (a light brown substance with very high viscosity), which is the cushioning compound of formula 1 (DVS-HPC).

[0085] Figure 1 This is a graph showing the NMR spectrum results of the cushioning compound prepared according to Synthesis Example 1. (Refer to...) Figure 1 It can be confirmed that the padding compound prepared according to Synthesis Example 1 includes vinylsilyl groups.

[0086] [Synthetic Example 2] Synthesis of the cushioning compound of Formula 5

[0087] The cushioning compound of Formula 1 (DVS-HPC, 50 mg), prepared according to Synthetic Example 1, 1,3,4,6-tetra(methoxymethyl)glycourea (20 mg), and pyridine p-toluenesulfonate (6 mg) were dissolved in propylene glycol monomethyl ether (PGME, 1 cm). 3A solution was prepared using the method described in Formula 5. This solution was then applied to an untreated silicon substrate (bare Si substrate) by spin-coating at approximately 1500 rpm for approximately 60 seconds to form a padding film (approximately 700 nm thick). The padding film was then heated at approximately 130°C for approximately 3 minutes to form a crosslinked padding film (approximately 600 nm thick) comprising the padding compound of Formula 5. The padding film and the crosslinked padding film were measured using attenuated total reflectance (ATR) spectroscopy with a Bruker VERTEX 80V infrared spectrometer.

[0088] Figure 2 This is a graph showing the Fourier transform infrared (FT-IR) spectrum of the pad film formed by synthesizing Example 2. (Refer to...) Figure 2 The presence of characteristic peaks of vinyl silane was confirmed in both the crosslinked pad film before and after the heating process.

[0089] [Experimental Example 1] Evaluation of the solubility of the cushioning compound of Formula 1

[0090] A solution (approximately 1.3 wt / vol%) obtained by dissolving the padding compound (DVC-HPC) of Formula 1 obtained according to Synthesis Example 1 in propylene glycol monomethyl ether (PGME) was applied to an untreated silicon substrate (bare Si substrate) by spin coating at approximately 3000 rpm for approximately 60 seconds, and then heated at approximately 80°C for approximately 1 minute. This formed a padding film (approximately 65 nm thick). The substrate with the padding film formed thereon was then immersed in PGME, propylene glycol monomethyl ether acetate (PGMEA), 2-heptanone, toluene, trifluorotoluene, methyl isobutyl ketone (MIBK), methanol, and water, respectively, for 1 minute and then dried. Subsequently, the substrate was processed using Kla-Tencor... The D-300 stylus profilometer measures the thickness of the padding film retained on the substrate.

[0091] [Experimental Example 2] Evaluation of the solubility of the cushioning compound of Formula 5

[0092] The cushioning compound of Formula 1 (DVS-HPC, 20 mg), prepared according to Synthetic Example 1, 1,3,4,6-tetra(methoxymethyl)glycourea (8 mg), and pyridine p-toluenesulfonate (2.4 mg) were dissolved in propylene glycol monomethyl ether (PGME, 1 cm). 3The solution was prepared by spin-coating the solution onto an untreated silicon substrate (bare Si substrate) at approximately 3000 rpm for approximately 60 seconds, followed by heating at approximately 130°C for approximately 3 minutes. This resulted in a cross-linked pad film (approximately 150 nm thick) comprising the pad compound of Formula 5. The substrate with the cross-linked pad film formed was then immersed in PGME, propylene glycol monomethyl ether acetate (PGMEA), 2-heptanone, toluene, trifluorotoluene, methyl isobutyl ketone (MIBK), cyclohexanone, methanol, isopropanol (IPA), and water for 1 minute and then dried. Subsequently, the solution was processed using Kla-Tencor's... The D-300 stylus profilometer measures the thickness of the cross-linked pad film retained on the substrate.

[0093] Figure 3 and Figure 4 This is a graph showing the evaluation results of the solubility of the cushioning compound according to an embodiment of the inventive concept.

[0094] Reference Figure 3 It can be confirmed that the cushion film (cushion compound of Formula 1) formed on the substrate according to Experimental Example 1 is soluble in polar organic solvents (e.g., PGME, PGMEA, 2-heptanone, MIBK, methanol, and water), but insoluble in hydrophobic solvents or aromatic solvents (e.g., toluene and trifluorotoluene). The cushion compound of Formula 1 may be hydrophilic; therefore, the cushion compound of Formula 1 may be insoluble in hydrophobic solvents or aromatic solvents.

[0095] Reference Figure 4 It can be confirmed that the cross-linked pad film (pad compound of Formula 5) formed on the substrate according to Experimental Example 2 is insoluble in polar organic solvents (e.g., 2-heptanone, MIBK, PGMEA, PGME, methanol, cyclohexanone, IPA, and water) as well as hydrophobic or aromatic solvents (e.g., toluene and trifluorotoluene). In other words, the pad compound of Formula 5 can be insoluble in hydrophobic or aromatic solvents as well as polar organic solvents.

[0096] The resist compounds according to embodiments of the inventive concept will be explained.

[0097] The resist compound according to embodiments of the inventive concept can be used in the manufacture of semiconductor devices and can be used in photolithography processes for manufacturing semiconductor devices. The resist compound can be used, for example, in extreme ultraviolet (EUV) lithography or electron beam lithography. Extreme ultraviolet (EUV) can refer to ultraviolet light having a wavelength of about 10 nm to about 124 nm, more specifically, ultraviolet light having a wavelength of about 13.0 nm to about 13.9 nm, and more specifically, ultraviolet light having a wavelength of about 13.4 nm to about 13.6 nm.

[0098] The resist compound may include alkylated metal oxide nanoclusters having a counter anion (or "balanced anion" or "coexisting anion"). The alkylated metal oxide nanoclusters may include a core structure comprising a metal oxide and an alkyl group of 1 to 20 carbon atoms bonded to the metal element of the core structure. The core structure may include a cation capable of forming an ionic bond with the counter anion. The counter anion may be an alkyl carboxylic acid anion of 2 to 20 carbon atoms, an alkyl ether alkyl carboxylic acid anion of 3 to 20 carbon atoms, an alkyl ether alkyl carboxylic acid anion of 4 to 20 carbon atoms, a fluoroalkyl carboxylic acid anion of 2 to 20 carbon atoms, a fluoroalkyl ether fluoroalkyl carboxylic acid anion of 3 to 20 carbon atoms, or a fluoroalkyl ether fluoroalkyl carboxylic acid anion of 4 to 20 carbon atoms.

[0099] The resist compound may include the structure of Formula 12.

[0100] [Equation 12]

[0101]

[0102] In Formula 12, M can be at least one selected from the group consisting of tin (Sn), zinc (Zn), lithium (Li), sodium (Na), potassium (K), beryllium (Be), magnesium (Mg), calcium (Ca), barium (Ba), aluminum (Al), silicon (Si), cadmium (Cd), mercury (Hg), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), germanium (Ge), palladium (Pd), platinum (Pt), lead (Pb), strontium (Sr), and manganese (Mn), and R is an alkyl group having 1 to 20 carbon atoms. - It is a counter anion and is an alkyl carboxylic acid anion with 2 to 20 carbon atoms, an alkyl ether alkyl carboxylic acid anion with 3 to 20 carbon atoms, an alkyl ether alkyl carboxylic acid anion with 4 to 20 carbon atoms, a fluoroalkyl carboxylic acid anion with 2 to 20 carbon atoms, a fluoroalkyl ether fluoroalkyl carboxylic acid anion with 3 to 20 carbon atoms, or a fluoroalkyl ether fluoroalkyl carboxylic acid anion with 4 to 20 carbon atoms. In the description, fluoroalkyl is an alkyl group in which at least one hydrogen atom is substituted by fluorine.

[0103] The resist compound may include alkylated tin oxide nanoclusters with counter anions. The alkylated tin oxide nanoclusters may include a core structure comprising a tin oxide and an alkyl group of 1 to 20 carbon atoms bonded to the tin element in the core structure. The core structure may include a cation and may form an ionic bond with the counter anion.

[0104] The resist compound may include, for example, the structure of formula 12-1.

[0105] [Equation 12-1]

[0106]

[0107] In equation 12-1, R is -CH2CH2CH2CH3, Rx - It is a counter anion and is a fluoroalkyl carboxylic acid anion with 2 to 20 carbon atoms, a fluoroalkyl ether fluoroalkyl carboxylic acid anion with 3 to 20 carbon atoms, or a fluoroalkyl ether fluoroalkyl carboxylic acid anion with 4 to 20 carbon atoms. Rx - It can have, for example, CF3 (CF2). a COO - CF3 (CF2) b CFCF3COO - CF3(CF2)2-O-CFCF3COO - or CF3(CF2)2-O-CFCF3CF2-O-CFCF3COO - (where "a" is an integer from 1 to 18, and "b" is an integer from 1 to 16) structure. Rx - It can have, for example, CF3(CF2)2-O-CFCF3COO - The structure.

[0108] The synthesis of the resist compound of Formula 12-1 can be carried out according to reaction 2.

[0109] [Reaction 2]

[0110]

[0111] [Synthetic Example 3] Synthesis of the resist compound of Formula 12-1 (Reaction 2)

[0112] At 100cm 3 In a small vial, tetramethylammonium hydroxide (TMAH) pentahydrate (5.78 g, 31.9 mmol) was dissolved in deionized water (DI water, 64 cm⁻¹). 3 The product was rapidly added to butyltin trichloride (3.0 g, 10.6 mmol) to form a first reaction solution. The first reaction solution was vigorously stirred at room temperature for approximately 1 hour, and the resulting product was filtered while being washed several times with DI water. The product was vacuum dried to obtain a white solid phase of alkylated tin oxide nanoclusters (BTOC, 1.8 g). Subsequently, the synthesized BTOC (0.4 g, 0.16 mmol) was dissolved in tetrahydrofuran (THF, 2 cm⁻¹). 3A second reaction solution was prepared by adding perfluoro(2-methyl-3-oxahexanoic acid) (0.11 g, 0.32 mmol) to a solution containing trifluorotoluene. The second reaction solution was stirred at approximately 50 °C for approximately 30 minutes to concentrate it. The concentrated substance was dissolved in trifluorotoluene (1.6 cm⁻¹). 3 The resulting material was injected into HFE-7500 (purchased from 3M) to form a precipitate, which was then filtered and recovered. The recovered material was vacuum dried to obtain a resist compound of formula 12-1 (H-BTOC) (0.3 g) as the final product, which was a white solid phase.

[0113] The resist compound may be hydrophobic and soluble in hydrophobic or aromatic solvents. The resist compound may include secondary electrons generated by light irradiation and free radicals generated by these secondary electrons. In embodiments, if the resist compound has a counterion (Rx) - If the fluoroalkyl carboxylic acid anion is present, the CF bond of the fluoroalkyl chain can be broken during the exposure process by secondary electrons generated via irradiation with light (e.g., extreme ultraviolet light), thus generating carbon radicals in the resist compound. These radicals (e.g., carbon radicals) in the resist compound can form chemical bonds with the vinylsilyl groups in the underlay compound. In embodiments, when the double bonds between carbon atoms in the vinylsilyl groups of the underlay compound break or open, the vinylsilyl groups in the underlay compound can combine with the radicals (e.g., carbon radicals) in the underlay compound.

[0114] The method for manufacturing a semiconductor device using a padding compound and a photoresist compound according to embodiments of the inventive concept will be explained.

[0115] Figures 5 to 8 This is a cross-sectional view illustrating a method for manufacturing a semiconductor device according to an embodiment of the inventive concept.

[0116] Reference Figure 5 A pad layer 110 may be formed on the lower layer 100, and a photoresist layer 120 may be formed on the pad layer 110. The lower layer 100 may be an etching target layer and may be formed of any material selected from semiconductor materials, conductive materials, insulating materials, and combinations thereof. The lower layer 100 may be formed as a single layer or may include stacked multilayers.

[0117] The padding layer 110 may include a hydrophilic padding compound. The padding compound may include a structure of Formula 1 or Formula 5. Formation of the padding layer 110 may include applying the padding compound onto the lower layer 100. In embodiments, the application of the padding compound may be performed by spin coating. In embodiments, the padding layer 110 may include a cellulose structure having at least one hydroxyl (-OH) group and at least one vinyl silyl group.

[0118] The photoresist layer 120 may include a hydrophobic resist compound. The resist compound may include the structure of Formula 12. Formation of the photoresist layer 120 may include applying the resist compound onto the pad layer 110. In embodiments, application of the resist compound may include spin-coating the resist compound onto the pad layer 110 using a hydrophobic solvent or an aromatic solvent. Formation of the photoresist layer 120 may also include performing a heating process (e.g., a soft baking process) on the applied resist compound.

[0119] According to embodiments of the inventive concept, a photoresist layer 120 can be formed by applying a photoresist compound to the pad 110 using a hydrophobic solvent or an aromatic solvent. The pad compound of Formula 1 may be insoluble in hydrophobic or aromatic solvents, and the pad compound of Formula 5 may be insoluble in both polar organic solvents and hydrophobic or aromatic solvents. Therefore, damage to the pad 110 can be prevented during the formation of the photoresist layer 120 using a hydrophobic or aromatic solvent.

[0120] Reference Figure 6 An exposure process can be performed on the photoresist layer 120. The exposure process may include arranging a photomask 130 on the photoresist layer 120 and irradiating the photoresist layer 120 with light 140 through the photomask 130. The light 140 may be an electron beam or extreme ultraviolet light. The photoresist layer 120 may include a first portion 122 exposed to the light 140 and a second portion 124 not exposed to the light 140. The light 140 can irradiate the first portion 122 through the opening 132 of the photomask 130, and may not irradiate the second portion 124 due to the obstruction of the photomask 130.

[0121] The resist compound may also include free radicals generated by irradiation with light 140. In embodiments, if the resist compound of formula 12 has a counter anion (Rx) - If ) is a fluoroalkyl carboxylic acid anion, then the CF bond of the fluoroalkyl chain can be broken by secondary electrons generated via irradiation light 140 to generate carbon radicals. In the first portion 122 of the photoresist layer 120, the resist compound may include radicals (e.g., carbon radicals) generated by irradiation light 140, and substances represented by Formula 12 can bind to each other via radicals (e.g., carbon radicals). Therefore, in the first portion 122 of the photoresist layer 120, the resist compound may include a cross-linked structure of substances represented by Formula 12. In the second portion 124 of the photoresist layer 120, the chemical structure of the resist compound may remain unchanged. As a result, a difference in solubility may exist between the first portion 122 and the second portion 124 after the exposure process.

[0122] Free radicals (e.g., carbon radicals) generated in the resist compound by irradiation with light 140 can form chemical bonds with vinyl silyl groups in the padding compound. In an embodiment, when the double bonds between the carbon atoms of the vinyl silyl groups in the padding compound break or open, the vinyl silyl groups in the padding compound can combine with free radicals (e.g., carbon radicals) in the resist compound. As a result, the first portion 122 of the photoresist layer 120 can be fixed to the padding layer 110 via chemical bonds, thus increasing the adhesion between the exposed photoresist layer 120 and the padding layer 110. In this case, the additional heating process (e.g., baking process) for fixing the photoresist layer 120 to the padding layer 110 can be omitted.

[0123] Reference Figure 7 After the exposure process, the photomask 130 can be removed. A development process can be performed on the exposed photoresist layer 120. The development process may include removing a second portion 124 of the photoresist layer 120 by using a hydrophobic solvent or an aromatic solvent. A first portion 122 of the photoresist layer 120 may be referred to as a photoresist pattern. The second portion 124 of the photoresist layer 120 can be selectively removed by the development process, and the photoresist pattern 122 may be a negative tone pattern.

[0124] According to embodiments of the inventive concept, a hydrophobic developing solution or an aromatic developing solution can be used to perform the developing process. The padding compound of Formula 1 may be insoluble in hydrophobic or aromatic solvents, and the padding compound of Formula 5 may be insoluble in both polar organic solvents and hydrophobic or aromatic solvents. Therefore, damage to the padding 110 can be prevented during the developing process using a hydrophobic or aromatic developing solution.

[0125] Reference Figure 8 The photoresist pattern 122 can be used as an etching mask to etch the pad layer 110 and the underlying layer 100. Etching of the pad layer 110 and the underlying layer 100 can include, for example, a wet etching process or a dry etching process. The pad layer 110 can be etched to form a pad layer pattern 110P, and the upper portion of the underlying layer 100 can be etched to form a lower pattern 100P. After forming the lower pattern 100P, the photoresist pattern 122 and the pad layer pattern 110P can be removed. The lower pattern 100P can be a semiconductor pattern, a conductive pattern, or an insulating pattern in a semiconductor device.

[0126] According to the inventive concept, the padding compound can be hydrophilic and insoluble in hydrophobic or aromatic solvents. The resist compound can be hydrophobic and soluble in hydrophobic or aromatic solvents. The photoresist layer 120 can be formed by applying the resist compound to the padding layer 110 using a hydrophobic or aromatic solvent, and the development process of the photoresist layer 120 can be performed using a hydrophobic or aromatic developing solution. Because the padding compound is insoluble in hydrophobic or aromatic solvents, damage to the padding layer 110 can be prevented during the formation and development processes of the photoresist layer 120.

[0127] Furthermore, the padding compound may include vinyl silyl groups, and the vinyl silyl groups of the padding compound may be chemically bonded to free radicals (e.g., carbon free radicals) generated in the resist compound. Therefore, the first portion 122 of the photoresist layer 120 (i.e., the photoresist pattern) can be fixed to the padding layer 110 via chemical bonds. As a result, the adhesion between the photoresist pattern 122 and the padding layer 110 can be increased, and the collapse of the photoresist pattern 122 can be suppressed. Furthermore, due to the increased adhesion between the photoresist pattern 122 and the padding layer 110, the dosage required for the exposure process to form the photoresist pattern 122 can be reduced. Therefore, the resolution and sensitivity of the photoresist pattern 122 can be improved.

[0128] The multilayer structure formed using a padding compound and a resist compound according to embodiments of the inventive concept will be explained.

[0129] According to some embodiments, such as reference Figure 5 The explained multilayer structure may include a lower layer 100, a padding layer 110, and a photoresist layer 120. Padding layer 110 may include a hydrophilic padding compound, and the padding compound may include the structure of Formula 1 or Formula 5. Photoresist layer 120 may include a hydrophobic resist compound, and the resist compound may include the structure of Formula 12.

[0130] According to some embodiments, such as reference Figure 6 The explained multilayer structure may include a lower layer 100, a pad layer 110, and a photoresist layer 120. The photoresist layer 120 may include a first portion 122 exposed to light 140 and a second portion 124 not exposed to light 140. In the first portion 122 of the photoresist layer 120, the resist compound may include free radicals generated by irradiation with light 140. In an embodiment, the counter anion (Rx) of the resist compound of Formula 12... -In the case where the molecule is a fluoroalkyl carboxylic acid anion, the first portion 122 of the photoresist layer 120 may include carbon radicals generated by irradiation with light 140. In the first portion 122 of the photoresist layer 120, substances represented by Formula 12 can bond with each other via free radicals (e.g., carbon radicals). Therefore, in the first portion 122 of the photoresist layer 120, the resist compound may include a cross-linked structure of substances represented by Formula 12. In the first portion 122 of the photoresist layer 120, free radicals (e.g., carbon radicals) can form chemical bonds with vinylsilyl groups in the padding compound. Therefore, the first portion 122 of the photoresist layer 120 can be fixed to the padding layer 110 via chemical bonds.

[0131] According to some embodiments, such as reference Figure 7 As explained, the multilayer structure may include a lower layer 100, a pad layer 110, and a photoresist pattern 122. The photoresist pattern 122 may be identical to the first portion 122 of the photoresist layer 120.

[0132] [Experimental Example 3] Formation of the underlay and photoresist layer

[0133] A solution (approximately 0.5 wt / vol%) of the padding compound (DVS-HPC) of Formula 1 synthesized in Synthesis Example 1, dissolved in propylene glycol monomethyl ether (PGME), was applied to an untreated silicon substrate (bare Si substrate) by spin-coating at approximately 3000 rpm for approximately 60 seconds, and then heated at approximately 80°C for approximately 1 minute to form a padding film (approximately 25 nm thick). Subsequently, an H-BTOC solution (approximately 2 wt / vol%) of the resist compound (H-BTOC) of Formula 12-1 synthesized in Synthesis Example 3, dissolved in trifluorotoluene, was applied to the padding film by spin-coating at approximately 3000 rpm for approximately 60 seconds, and then heated at approximately 80°C for approximately 1 minute to form a photoresist film (approximately 75 nm thick). After stacking the padding film and the photoresist film, the thickness of the multilayer film was confirmed to be approximately 100 nm.

[0134] Figure 9 Atomic force microscopy images showing the results of surface roughness measurements of the pad film and photoresist film formed according to Experimental Example 3 are shown.

[0135] Reference Figure 9 The surface roughness of the pad film formed according to Experimental Example 3 was measured using atomic force microscopy, and it was confirmed that a uniform film with an RMS roughness value of about 1.3 nm was formed. Subsequently, the surface roughness of the photoresist film formed on the pad film according to Experimental Example 3 was measured using atomic force microscopy, and it was confirmed that a uniform film with an RMS roughness value of about 0.48 nm was formed.

[0136] [Experimental Example 4] Evaluation of the solubility change of photoresist films based on electron beam dose

[0137] 1) Forming a photoresist pattern on a substrate without a backing layer (comparative example)

[0138] A solution (approximately 1.8 wt / vol%) of the resist compound of formula 12-1 synthesized in Synthesis Example 3, dissolved in trifluorotoluene, was applied to an untreated silicon substrate by spin-coating at approximately 1500 rpm for approximately 60 seconds, and then heated at approximately 80 °C for approximately 1 minute to form a photoresist film (approximately 80 nm thick). The photoresist film was then irradiated with an accelerating voltage of approximately 80 keV at an acceleration of approximately 50 μC / cm. 2 Approximately 1500 μC / cm 2 An electron beam was used. A development process was performed using trifluorotoluene for approximately 60 seconds to form a negative photoresist pattern. Afterwards, a photoresist pattern manufactured by Kla-Tencor was used. The D-300 stylus profilometer measures the thickness of the remaining photoresist pattern and evaluates the solubility change properties.

[0139] 2) Forming a photoresist pattern on a substrate coated with a pad (experimental example)

[0140] On the multilayer thin film formed in Experimental Example 3, irradiation with approximately 50 μC / cm was carried out at an accelerating voltage of approximately 80 keV. 2 Approximately 1500 μC / cm 2 An electron beam was used. A development process was performed using trifluorotoluene for approximately 60 seconds to form a negative photoresist pattern. Afterwards, a photoresist pattern manufactured by Kla-Tencor was used. The D-300 stylus profilometer measures the thickness of the remaining photoresist pattern and evaluates the solubility change properties.

[0141] Figure 10 This is a graph showing the evaluation results of the solubility change of the photoresist film according to Experimental Example 4.

[0142] Reference Figure 10 In the case of an untreated silicon substrate (bare) (comparative example), when approximately 580 μC / cm 2 When an electron beam is irradiated onto a photoresist film, the thickness of the photoresist pattern can be maintained at approximately 50% of the thickness of the photoresist film. In the case of a substrate coated with a pad (experimental example), when approximately 340 μC / cm² is applied... 2When an electron beam irradiates a photoresist film, the thickness of the photoresist pattern can be maintained at approximately 50% of the thickness of the photoresist film. In other words, it can be demonstrated that negative photoresist patterns can be formed on a substrate coated with a pad using a relatively small electron beam dose.

[0143] [Experimental Example 5] The formation of photoresist patterns based on electron beam irradiation

[0144] 1) Forming a photoresist pattern on a substrate without a backing layer (comparative example)

[0145] A solution of the resist compound (H-BTOC) of Formula 12-1 synthesized in Synthesis Example 3, dissolved in trifluorotoluene, was applied to an untreated silicon substrate by spin-coating at approximately 1500 rpm for approximately 60 seconds, and then heated at approximately 80 °C for approximately 1 minute to form a photoresist film (approximately 80 nm thick). The photoresist film was then irradiated with an accelerating voltage of approximately 80 keV at approximately 50 μC / cm². 2 Approximately 1500 μC / cm 2 The electron beam. A development process is performed using trifluorotoluene for about 30 seconds to form a negative photoresist pattern with a linewidth of about 50 nm to about 100 nm.

[0146] 2) Forming a photoresist pattern on a substrate coated with a pad (experimental example)

[0147] On the multilayer thin film formed in Experimental Example 3, irradiation with approximately 50 μC / cm was carried out at an accelerating voltage of approximately 80 keV. 2 Approximately 1500 μC / cm 2 The electron beam. A development process is performed using trifluorotoluene for about 30 seconds to form a negative photoresist pattern with a linewidth of about 50 nm to about 100 nm.

[0148] Figure 11 A scanning electron microscope image of the photoresist pattern formed according to Experimental Example 5 is shown.

[0149] Reference Figure 11 In the case of an untreated silicon substrate (bare) (comparative example), when irradiated with approximately 1350 μC / cm²... 2 When exposed to an electron beam, a negative photoresist pattern with a linewidth of approximately 70 nm (CD = 70 nm) is formed. In the case of a substrate coated with a pad (experimental example), when irradiated with approximately 800 μC / cm², a negative photoresist pattern is formed. 2 When the electron beam is applied, a negative photoresist pattern with a linewidth of approximately 70 nm is formed. In other words, it can be demonstrated that, in the case of a substrate coated with a pad, a negative photoresist pattern can be formed using a relatively small electron beam dose.

[0150] [Experimental Example 6] Evaluation of the solubility change of photoresist films based on extreme ultraviolet radiation dose

[0151] 1) Forming a photoresist pattern on a substrate coated with DVS (comparative example)

[0152] A solution of 1,3-divinyltetramethyldisilazane (DVS) dissolved in propylene glycol monomethyl ether acetate (PGMEA) (approximately 20 wt / vol%) was applied to an untreated silicon substrate (bare Si substrate) by spin-coating at approximately 3000 rpm for approximately 30 seconds, and then heated at approximately 110 °C for approximately 1 minute to coat the silicon substrate with DVS. Subsequently, on the DVS-coated silicon substrate, an H-BTOC solution of the resist compound of formula 12-1 synthesized in Synthesis Example 3 (approximately 0.9 wt / vol%) dissolved in trifluorotoluene was applied by spin-coating at approximately 3000 rpm for approximately 60 seconds, and then heated at approximately 80 °C for approximately 1 minute to form a photoresist film (approximately 23 nm thick). Subsequently, extreme ultraviolet (EUV) radiation (approximately 2 mJ / cm²) was applied to the photoresist film using a MET5 stepper from Lawrence Berkeley National Laboratory in America. 2 Approximately 80 mJ / cm 2 The dosage was adjusted, and a development process was performed using trifluorotoluene for approximately 20 seconds to form a negative photoresist pattern. Afterwards, a photoresist pattern manufactured by Kla-Tencor was applied. The D-300 stylus profilometer measures the thickness of the remaining photoresist pattern and evaluates the solubility change properties of the photoresist film.

[0153] 2) Forming a photoresist pattern on a substrate coated with a padding layer (DVS-HPC) (experimental example)

[0154] A solution (approximately 0.5 wt / vol%) of the padding compound (DVS-HPC) of Formula 1 synthesized in Synthesis Example 1, dissolved in propylene glycol monomethyl ether (PGME), was applied to an untreated silicon substrate (bare Si substrate) by spin-coating at approximately 3000 rpm for approximately 60 seconds, and heated at approximately 80°C for approximately 1 minute to form a padding film (approximately 23 nm thick). Subsequently, a solution (approximately 0.9 wt / vol%) of the resist compound (H-BTOC) of Formula 12-1 synthesized in Synthesis Example 3, dissolved in trifluorotoluene, was applied to the padding film by spin-coating at approximately 3000 rpm for approximately 60 seconds, and heated at approximately 80°C for approximately 1 minute to form a photoresist film (approximately 23 nm thick). Then, the photoresist film was irradiated with extreme ultraviolet (EUV) light (approximately 1 mJ / cm²) using a MET5 stepper belonging to Lawrence Berkeley National Laboratory, USA.2 Up to 40 mJ / cm 2 The dosage was adjusted, and a development process was performed using trifluorotoluene for approximately 20 seconds to form a negative photoresist pattern. Afterwards, a photoresist pattern manufactured by Kla-Tencor was applied. The D-300 stylus profilometer measures the thickness of the remaining photoresist pattern and evaluates the solubility change properties of the photoresist film.

[0155] Figure 12 This is a graph showing the evaluation results of the solubility change of the photoresist film according to Experimental Example 6.

[0156] Reference Figure 12 In the case of a silicon substrate coated with DVS (comparative example), when approximately 16.3 mJ / cm 2 When extreme ultraviolet light is irradiated onto a photoresist film, the thickness of the photoresist pattern can be maintained at approximately 50% of the thickness of the photoresist film. In the case of a substrate coated with a pad (DVS-HPC) (experimental example), when approximately 8.9 mJ / cm² is applied... 2 When extreme ultraviolet light is irradiated onto a photoresist film, the thickness of the photoresist pattern can be maintained at approximately 50% of the thickness of the photoresist film. In other words, in the case of a substrate coated with a pad (DVS-HPC), it can be demonstrated that a negative photoresist pattern can be formed using a relatively small dose of extreme ultraviolet light.

[0157] According to the inventive concept, the padding compound can be hydrophilic and insoluble in hydrophobic or aromatic solvents. The resist compound can be hydrophobic and soluble in hydrophobic or aromatic solvents. The photoresist layer 120 can be formed by applying the resist compound to the padding layer 110 using a hydrophobic or aromatic solvent, and the development process of the photoresist layer 120 can be performed using a hydrophobic or aromatic developing solution. Because the padding compound is insoluble in hydrophobic or aromatic solvents, damage to the padding layer 110 can be prevented during the formation and development processes of the photoresist layer 120.

[0158] Furthermore, when the padding compound includes the structure of Formula 5, the padding compound may be insoluble in polar organic solvents as well as hydrophobic solvents or aromatic solvents. Therefore, during the formation and development process of the photoresist layer 120, the degree of freedom in selecting the solvent or developing solution used for coating can be increased.

[0159] Furthermore, the padding compound may include vinyl silyl groups, and the vinyl silyl groups of the padding compound can form chemical bonds with free radicals (e.g., carbon free radicals) generated in the resist compound. Therefore, the adhesion between the photoresist pattern 122 and the padding layer 110 can be increased, and the collapse of the photoresist pattern 122 can be suppressed. Additionally, due to the increased adhesion between the photoresist pattern 122 and the padding layer 110, the dosage required during the exposure process for forming the photoresist pattern 122 can be reduced. As a result, the resolution and sensitivity of the photoresist pattern 122 can be improved.

[0160] Therefore, it is possible to provide resist compounds and padding compounds that can improve the resolution and sensitivity of photoresist patterns and suppress the collapse of photoresist patterns, multilayer structures formed using the resist compounds and padding compounds, and methods for manufacturing semiconductor devices using the resist compounds and padding compounds.

[0161] According to the inventive concept, the padding compound can be hydrophilic and insoluble in hydrophobic or aromatic solvents. The resist compound can be hydrophobic and soluble in hydrophobic or aromatic solvents. Therefore, damage to the padding layer can be prevented during the formation of the photoresist layer using hydrophobic or aromatic solvents and during the development process using hydrophobic or aromatic developing solutions.

[0162] Furthermore, the padding compound may include vinyl silyl groups, and the vinyl silyl groups of the padding compound can form chemical bonds with free radicals (e.g., carbon free radicals) generated in the resist compound. Therefore, the adhesion between the photoresist pattern and the padding layer can be increased, and the collapse of the photoresist pattern can be suppressed. Moreover, due to the increased adhesion between the photoresist pattern and the padding layer, the dosage required during the exposure process for forming the photoresist pattern can be reduced, resulting in improved resolution and sensitivity of the photoresist pattern.

[0163] Therefore, it is possible to provide resist compounds and padding compounds that can improve the resolution and sensitivity of photoresist patterns and suppress the collapse of photoresist patterns, multilayer structures formed using the resist compounds and padding compounds, and methods for manufacturing semiconductor devices using the resist compounds and padding compounds.

[0164] Although embodiments of the invention have been described, it is understood that the invention should not be limited to the embodiments, but that various changes and modifications can be made by those skilled in the art within the spirit and scope of the invention as claimed.

Claims

1. A padding compound for photolithography, said padding compound comprising the structure of Formula 1: Formula 1 In Equation 1, R1, R2, and R3 are each independently hydrogen, deuterium, or functional groups represented by Equation 2, Equation 3, or Equation 4 below, and n is an integer from 2 to 10000. In Equation 1, at least one of R1, R2, and R3 is a functional group represented by Equation 3 or Equation 4: Formula 2 Formula 3 Formula 4 In equations 2 and 4, m is an integer from 1 to 20. In Formulas 3 and 4, R4, R5, R6, R7, and R8 are each independently hydrogen, deuterium, or an alkyl group with one to three carbon atoms, and In equations 2 to 4, It is the part that combines with oxygen in Formula 1.

2. The pad compound for photolithography according to claim 1, wherein, The cushioning compound is hydrophilic.

3. The pad compound for photolithography according to claim 1, wherein, In Equation 1, the other of R1, R2 and R3 is hydrogen, deuterium or a functional group represented by Equation 2.

4. The pad compound for photolithography according to claim 1, wherein, The cushioning compound comprises a structure in which the substance represented by Formula 1 is cross-linked by using tetra(methoxymethyl)glycourea as a curing agent.

5. A photoresist compound for photolithography, said photoresist compound comprising alkylated metal oxide nanoclusters having counter-anion resistance, wherein, Alkylated metal oxide nanoclusters comprise a core structure containing a metal oxide and an alkyl group of 1 to 20 carbon atoms bonded to the metal element of the core structure. The counter anions are fluoroalkyl carboxylic acid anions with 2 to 20 carbon atoms, fluoroalkyl ether fluoroalkyl carboxylic acid anions with 3 to 20 carbon atoms, or fluoroalkyl ether fluoroalkyl carboxylic acid anions with 4 to 20 carbon atoms.

6. The photoresist compound for photolithography according to claim 5, wherein, The corrosion resist compound comprises the structure of Formula 12: Formula 12 In Formula 12, M is at least one selected from the group consisting of tin, zinc, lithium, sodium, potassium, beryllium, magnesium, calcium, barium, aluminum, silicon, cadmium, mercury, chromium, iron, cobalt, nickel, copper, germanium, palladium, platinum, lead, strontium, and manganese. R is an alkyl group with 1 to 20 carbon atoms, and Rx - It is a counter anion and is a fluoroalkyl carboxylic acid anion with 2 to 20 carbon atoms, a fluoroalkyl ether fluoroalkyl carboxylic acid anion with 3 to 20 carbon atoms, or a fluoroalkyl ether fluoroalkyl carboxylic acid anion with 4 to 20 carbon atoms.

7. The photoresist compound for photolithography according to claim 6, wherein, In Equation 12, M is tin, and R is -CH2CH2CH2CH3.

8. The photoresist compound for photolithography according to claim 7, wherein Rx - It has CF3 (CF2) a COO - CF3 (CF2) b CFCF3COO - CF3(CF2)2-O-CFCF3COO - or CF3(CF2)2-O-CFCF3CF2-O-CFCF3COO - The structure, a is an integer from 1 to 18, and b is an integer from 1 to 16.

9. The photoresist compound for photolithography according to claim 6, wherein, The corrosion inhibitor compound is hydrophobic.

10. A multilayer structure, the multilayer structure comprising: Lower layer; The subbase layer is located on top of the lower layer; as well as The photoresist layer is located on the padding layer, wherein, The padding layer comprises a cellulose structure having at least one hydroxyl group and at least one vinyl silyl group, and The photoresist layer comprises alkylated metal oxide nanoclusters with counter-anion properties, wherein the alkylated metal oxide nanoclusters include a core structure comprising a metal oxide and an alkyl group of 1 to 20 carbon atoms bonded to the metal element of the core structure. The counter anions are fluoroalkyl carboxylic acid anions with 2 to 20 carbon atoms, fluoroalkyl ether fluoroalkyl carboxylic acid anions with 3 to 20 carbon atoms, or fluoroalkyl ether fluoroalkyl carboxylic acid anions with 4 to 20 carbon atoms.

11. The multilayer structure according to claim 10, wherein, The cushioning layer includes a cushioning compound, which has the structure of Formula 1 below: Formula 1 In Equation 1, R1, R2, and R3 are each independently hydrogen, deuterium, or functional groups represented by Equation 2, Equation 3, or Equation 4 below, and n is an integer from 2 to 10000: Formula 2 Formula 3 Formula 4 In equations 2 and 4, m is an integer from 1 to 20. In Formulas 3 and 4, R4, R5, R6, R7, and R8 are each independently hydrogen, deuterium, or an alkyl group with one to three carbon atoms, and In equations 2 to 4, It is the part that combines with oxygen in Formula 1.

12. The multilayer structure according to claim 11, wherein, In Equation 1, at least one of R1, R2 and R3 is a functional group represented by Equation 3 or Equation 4.

13. The multilayer structure according to claim 12, wherein, In Equation 1, the other of R1, R2 and R3 is hydrogen, deuterium or a functional group represented by Equation 2.

14. The multilayer structure according to claim 11, wherein, The underlayment compound includes a structure in which the substance represented by Formula 1 is cross-linked by using tetra(methoxymethyl)glycourea as a curing agent.

15. The multilayer structure according to claim 10, wherein, The photoresist layer includes a photoresist compound, which has a structure of Formula 12: Formula 12 In Formula 12, M is at least one selected from the group consisting of tin, zinc, lithium, sodium, potassium, beryllium, magnesium, calcium, barium, aluminum, silicon, cadmium, mercury, chromium, iron, cobalt, nickel, copper, germanium, palladium, platinum, lead, strontium, and manganese. R is an alkyl group with 1 to 20 carbon atoms, and Rx - It is a counter anion and is a fluoroalkyl carboxylic acid anion with 2 to 20 carbon atoms, a fluoroalkyl ether fluoroalkyl carboxylic acid anion with 3 to 20 carbon atoms, or a fluoroalkyl ether fluoroalkyl carboxylic acid anion with 4 to 20 carbon atoms.

16. The multilayer structure according to claim 15, wherein, The resist compound also includes carbon free radicals, and The carbon radicals of the resist compound form chemical bonds with the vinyl silyl group of the padding layer.

17. A method for manufacturing a semiconductor device, the method comprising the following steps: A cushion layer is formed on the lower layer; and A photoresist layer is formed on the padding layer. The step of forming the photoresist layer includes applying the photoresist compound to the pad layer using a hydrophobic solvent or an aromatic solvent. The padding layer includes padding compounds with hydrophilic properties. The cushioning compound comprises a cellulose structure having at least one hydroxyl group and at least one vinyl silyl group. The resist compounds include alkylated metal oxide nanoclusters with counter anions. Alkylated metal oxide nanoclusters comprise a core structure containing a metal oxide and an alkyl group of 1 to 20 carbon atoms bonded to the metal element of the core structure. The counter anions are fluoroalkyl carboxylic acid anions with 2 to 20 carbon atoms, fluoroalkyl ether fluoroalkyl carboxylic acid anions with 3 to 20 carbon atoms, or fluoroalkyl ether fluoroalkyl carboxylic acid anions with 4 to 20 carbon atoms.

18. The method for manufacturing a semiconductor device according to claim 17, wherein, The cushioning compound includes the structure of Formula 1 below: Formula 1 In Equation 1, R1, R2, and R3 are each independently hydrogen, deuterium, or functional groups represented by Equation 2, Equation 3, or Equation 4 below, and n is an integer from 2 to 10000: Formula 2 Formula 3 Formula 4 In equations 2 and 4, m is an integer from 1 to 20. In Formulas 3 and 4, R4, R5, R6, R7, and R8 are each independently hydrogen, deuterium, or an alkyl group with one to three carbon atoms, and In equations 2 to 4, It is the part that combines with oxygen in Formula 1.

19. The method for manufacturing a semiconductor device according to claim 18, wherein, The underlayment compound includes a structure in which the substance represented by Formula 1 is cross-linked by using tetra(methoxymethyl)glycourea as a curing agent.

20. The method for manufacturing a semiconductor device according to claim 17, wherein, The resist compound includes the structure of formula 12: Formula 12 In Formula 12, M is at least one selected from the group consisting of tin, zinc, lithium, sodium, potassium, beryllium, magnesium, calcium, barium, aluminum, silicon, cadmium, mercury, chromium, iron, cobalt, nickel, copper, germanium, palladium, platinum, lead, strontium, and manganese. R is an alkyl group with 1 to 20 carbon atoms, and Rx - It is a counter anion and is a fluoroalkyl carboxylic acid anion with 2 to 20 carbon atoms, a fluoroalkyl ether fluoroalkyl carboxylic acid anion with 3 to 20 carbon atoms, or a fluoroalkyl ether fluoroalkyl carboxylic acid anion with 4 to 20 carbon atoms.

21. The method for manufacturing a semiconductor device according to claim 17, the method further comprising performing an exposure process on a photoresist layer. in, The exposure process is performed using an electron beam or extreme ultraviolet light.

22. The method for manufacturing a semiconductor device according to claim 21, wherein, The photoresist layer comprises a first portion exposed by the exposure process and a second portion not exposed by the exposure process. In the first part of the photoresist layer, the resist compound includes carbon free radicals generated by an electron beam or extreme ultraviolet light, and In the first part of the photoresist layer, the carbon radicals of the resist compound form chemical bonds with the vinylsilyl groups of the padding compound.

23. The method for manufacturing a semiconductor device according to claim 22, the method further comprising a second portion of performing a developing process to selectively remove the photoresist layer. in, The developing process is performed using a hydrophobic developing solution or an aromatic developing solution.

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