Multilayer molecular film photoresist with molecular beam structure containing organic monomolecules having crosslinkable functional groups and method for producing the same

Abstract

A multilayer molecular film photoresist is provided, which comprises a plurality of molecular beams arranged laterally above a substrate, each of which includes linearly linked monomolecules represented by the following Chemical Formula 1: JPEG2026506378000030.jpg11128In Chemical Formula 1, one of the *'s is a bond to a functional group in a lower monolayer, and the other is a bond to a functional group in an upper monolayer, OM is an organic monolayer, MM is a main inorganic monolayer containing a metal atom, m is 1 to 2, n is 1 to 2, and l is 1 to 1000.A lateral inorganic monolayer having a metal atom is located between the molecular beams and is bonded to the side of the organic monolayer (OM) in one of the molecular beams, and a crosslinkable functional group bonded to the side of the organic monolayer (OM) is located in the other molecular beam.

Description

[Technical Field]

[0001] The present invention relates to photoresists, and more particularly to EUV photoresists. [Background technology]

[0002] Photoresists have been the subject of continuous research, with the most active research being into the method of manufacturing a liquid photosensitive solution and then spin-coating it onto a substrate. The most commonly used conventional photoresists are chemically amplified photoresists (CARs), which contain a polymer resin, a photo-acid generator (PAG), and a base (quencher).

[0003] In recent years, the semiconductor industry has introduced extreme ultraviolet (EUV) exposure technology (photolithography) that uses an EUV light source, making it possible to form ultrafine patterns of 10 nm or less.

[0004] However, EUV has a photon density that is 1 / 14 that of 193 nm DUV (deep UV), which can induce stochastic failures, specifically photon shot noise. For example, in the case of CAR, the low photon density reduces the probability of PAG reaction, which can lead to shot noise. In addition, CAR is known to have the drawback of exhibiting relatively large line edge roughness due to the large size of polymer resin particles, which are 4 nm or larger. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, an object of the present invention is to provide a photoresist having excellent photon absorption and low line edge roughness, and a method for manufacturing the same.

[0006] The technical problems of the present invention are not limited to the above-mentioned technical problems, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description. [Means for solving the problem]

[0007] According to a first embodiment of the present invention, there is provided a multilayer molecular film photoresist, which comprises a plurality of molecular beams arranged laterally above a substrate, each of which includes linearly linked monomolecules represented by the following Chemical Formula 1:

[0008] [ka]

[0009] In the above Chemical Formula 1, one of the *'s is a bond to a functional group in the lower monolayer, and the other is a bond to a functional group in the upper monolayer; OM is an organic monolayer; MM is a mainly inorganic monolayer containing a metal atom; m is 1 to 2; n is 1 to 2; and l is 1 to 1000.

[0010] The molecular beam is positioned between the molecular beams and includes a lateral inorganic monomolecule having a metal atom, which is bonded to a side of the organic monomolecule (OM) in one of the molecular beams, and a crosslinkable functional group, which is bonded to a side of the organic monomolecule (OM) in the other molecular beam.

[0011] Van der Waals interactions may exist between the organic monomolecules in the laterally adjacent molecular beams.

[0012] The main inorganic monomer may be an inorganic monomer represented by the following chemical formula 2:

[0013] [ka]

[0014] In the formula 2, one of the * may be a bond to a functional group in the lower monomer, and the other may be a bond to a functional group in the upper monomer. a may be O, S, Se, NR (R is H or CH3), or PR (R is H or CH3). M 0 The metal atom may be Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W, or Si. Z1 and Z2 may each independently be a direct bond, a C1-C20 substituted or unsubstituted linear or branched alkylene group, a C1-C20 substituted or unsubstituted linear or branched alkylene oxide, a C1-C20 substituted or unsubstituted linear or branched alkylene amino, a C1-C20 substituted or unsubstituted linear or branched alkylene silyl amino, a C1-C20 substituted or unsubstituted linear or branched alkylene thio, a C1-C20 substituted or unsubstituted linear or branched alkylene seleno, or a C1-C20 substituted or unsubstituted linear or branched alkylene phosphino. L a and L b may be each independently a halogen group, a C1-C5 alkyl group, a C1-C5 alkylsilylamino group, a C1-C5 alkoxy group, a C1-C5 alkylthio group, a C1-C5 alkylseleno group, a C1-C5 alkylamino group, a C1-C5 alkylphosphino group, acetate, or allyloxy. The sum of na and nb may be an integer of 0 to 4. In one example, both na and nb may be 0.

[0015] The side inorganic monomer may be an inorganic monomer represented by the following chemical formula 3:

[0016] [ka]

[0017] In the above Chemical Formula 3, * represents a bond to the organic monomolecule, and X c is O, S, Se, NR (R is H or CH3) or PR (R is H or CH3), and M 0 The metal atom may be Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W, or Si. Z1 and Z2 may each independently be a direct bond, a C1-C20 substituted or unsubstituted linear or branched alkylene group, a C1-C20 substituted or unsubstituted linear or branched alkylene oxide, a C1-C20 substituted or unsubstituted linear or branched alkylene amino, a C1-C20 substituted or unsubstituted linear or branched alkylene silyl amino, a C1-C20 substituted or unsubstituted linear or branched alkylene thio, a C1-C20 substituted or unsubstituted linear or branched alkylene seleno, or a C1-C20 substituted or unsubstituted linear or branched alkylene phosphino. L a and L b may each independently be a halogen group, a C1-C5 alkyl group, a C1-C5 alkylsilylamino group, a C1-C5 alkoxy group, a C1-C5 alkylthio group, a C1-C5 alkylseleno group, a C1-C5 alkylamino group, a C1-C5 alkylphosphino group, acetate, or allyloxy. The sum of na and nb may be an integer of 0 to 4. R b2 may be a halogen group (e.g., Cl, Br, or I), a C1-C5 alkyl group, a C1-C5 alkylsilylamino group, a C1-C5 alkoxy, a C1-C5 alkylthio group, a C1-C5 alkylseleno group, a C1-C5 alkylamino group, or a C1-C5 alkylphosphino group. In one example, both na and nb may be 0.

[0018] The crosslinkable functional group is *-Z5X c R a3 where * is a bond to the organic monolayer, Z5 is a direct bond or a C1 to C5, specifically a C1 to C3, substituted or unsubstituted, linear or branched alkylene group, and X cis O, S, Se, NR (R is H or CH3) or PR (R is H or CH3), and R a3 may be hydrogen or a C1-C2 alkyl group.

[0019] The organic monomer is represented by the following chemical formula 4.

[0020] [ka]

[0021] In the formula 4, one of the * may be a bond to a functional group in the lower monomer, and the other may be a bond to a functional group in the upper monomer. b may be O, S, Se, NR (R is H or CH3), or PR (R is H or CH3). Z3 and Z4 may each independently be a direct bond or a C1 to C5 linear or branched alkylene group. MR is a skeleton having a linear chain with 2 to 7 carbons or a non-aromatic or aromatic ring with 3 to 18 carbons, and the side inorganic monomer or the crosslinkable functional group may be bonded to the skeleton (MR). In one example, MR may be a C2 to C6 linear alkylene group.

[0022] According to a second embodiment of the present invention, there is provided a multilayer molecular film photoresist. The multilayer molecular film photoresist comprises a plurality of molecular beams arranged laterally above a substrate, each of which includes linearly linked monomolecules, each of which includes a plurality of main inorganic monomolecules containing a metal atom and an organic monomolecule linked between at least some of the main inorganic monomolecules. The multilayer molecular film photoresist further includes a side inorganic monomolecule containing a metal atom, which is located between the molecular beams and bonded to a side of the organic monomolecule.

[0023] The main inorganic monolayer and the organic monolayer located within the molecular beam may be connected by a bond selected from the group consisting of -O-, -S-, -Se-, -NR- (R is H or CH3), and -PR- (R is H or CH3) contained in any of these monolayers. The organic monolayer and the side inorganic monolayer may be connected by a bond selected from the group consisting of -O-, -S-, -Se-, -NR- (R is H or CH3), and -PR- (R is H or CH3) contained in any of these monolayers.

[0024] The metal atoms contained in the main inorganic monolayer or the side inorganic monolayer may be Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Ti, Cu, W, or Si. Van der Waals interactions may exist between the organic monolayers in molecular beams adjacent to each other in the horizontal direction of the molecular beam. Each molecular beam may be formed by alternately stacking and bonding the main inorganic monolayer and the organic monolayer. The multilayer molecular film photoresist may be an EUV photoresist.

[0025] According to a third embodiment of the present invention, there is provided a method for manufacturing a photoresist pattern. First, a multilayer molecular film photoresist is provided. The multilayer molecular film photoresist comprises a plurality of molecular beams arranged laterally above a substrate, each of which includes linearly linked monomolecules represented by the following Chemical Formula 1:

[0026] [ka]

[0027] In the above Chemical Formula 1, one of the *'s is a bond to a functional group in the lower monolayer, and the other is a bond to a functional group in the upper monolayer; OM is an organic monolayer; MM is a mainly inorganic monolayer containing a metal atom; m is 1 to 2; n is 1 to 2; and l is 1 to 1000.

[0028] The inorganic monolayer is positioned between the molecular beams and is bonded to the side of the organic monolayer (OM) in one of the molecular beams, and includes a side inorganic monolayer having a metal atom and a crosslinkable functional group bonded to the side of the organic monolayer (OM) in the other molecular beam.

[0029] Then, a portion of the multilayer molecular film photoresist is irradiated with radiation such as E-beam or EUV to crosslink the inorganic monomers on the side with the crosslinkable functional groups, and the portion of the multilayer molecular film photoresist not exposed to the radiation is developed and removed.

[0030] According to a fourth embodiment of the present invention, there is provided a method for manufacturing a photoresist pattern. The method for manufacturing a photoresist pattern includes loading a substrate into a chamber having a gas inlet and a gas outlet. An organic precursor subcycle is performed by supplying an organic precursor represented by the following Chemical Formula 5 into the chamber with the gas outlet closed, reacting the organic precursor on the substrate, and purging any remaining reaction gas from the chamber. An inorganic precursor subcycle is performed by supplying an inorganic precursor represented by the following Chemical Formula 6 into the chamber with the gas outlet closed, reacting the inorganic precursor on the organic precursor, and purging any remaining reaction gas from the chamber. A unit cycle including the organic precursor subcycle and the inorganic precursor subcycle is performed several times to form a multilayer molecular film photoresist. E-beam or EUV radiation is irradiated onto a portion of the multilayer molecular film photoresist. The regions of the multilayer molecular film photoresist not exposed to the radiation are developed and removed.

[0031] [ka]

[0032] In the above formula 5, R a1 , R a2 , and R a3 are each independently hydrogen or a C1-C2 alkyl group, and X a , X b , and X Care each independently O, S, Se, NR (R is H or CH3) or PR (R is H or CH3); Z3, Z4, and Z5 are each independently a direct bond or a C1-C3 substituted or unsubstituted linear or branched alkylene group; MR is a linear chain having 2 to 7 carbons or a skeleton having a non-aromatic or aromatic ring having 3 to 18 carbons; and x may be 1 or 2.

[0033] [ka]

[0034] In Chemical Formula 6, R b1 and R b2 are each independently a halogen group, a C1-C5 alkyl group, a C1-C5 alkylsilylamino group, a C1-C5 alkoxy group, a C1-C5 alkylthio group, a C1-C5 alkylseleno group, a C1-C5 alkylamino group, or a C1-C5 alkylphosphino group, and M 0 is Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W, or Si; Z1 and Z2 are each independently a direct bond, a C1-C20 substituted or unsubstituted linear or branched alkylene group, a C1-C20 substituted or unsubstituted linear or branched alkylene oxide, a C1-C20 substituted or unsubstituted linear or branched alkylene amino, a C1-C20 substituted or unsubstituted linear or branched alkylene silyl amino, a C1-C20 substituted or unsubstituted linear or branched alkylene thio, a C1-C20 substituted or unsubstituted linear or branched alkylene seleno, or a C1-C20 substituted or unsubstituted linear or branched alkylene phosphino; L a and L b are each independently a halogen group, a C1-C5 alkyl group, a C1-C5 alkylsilylamino group, a C1-C5 alkoxy group, a C1-C5 alkylthio group, a C1-C5 alkylseleno group, a C1-C5 alkylamino group, a C1-C5 alkylphosphino group, acetate, or allyloxy, and the sum of na and nb is an integer of 0 to 4. [Effects of the Invention]

[0035] The multilayer molecular film photoresist according to an embodiment of the present invention can separate molecular beams instead of particles during exposure and development, thereby reducing line edge roughness (LER), which refers to the side roughness of a pattern, and improving resolution.

[0036] Furthermore, in one example, the multilayer molecular film photoresist contains metal atoms with extremely high light absorption rate for EUV, and thus can exhibit low stochastic failure and high photosensitivity even for EUV, which has a low photon density.

[0037] In addition, the molecular beams are formed so as to include a side inorganic monomolecule having a metal atom, which is positioned between the molecular beams and bonded to a side of an organic monomolecule in one of the molecular beams, and a crosslinkable functional group bonded to a side of the organic monomolecule in the other molecular beam, and upon irradiation with radiation, the terminal unreacted functional group of the side inorganic monomolecule further reacts with the organic monomolecule and is crosslinked, thereby forming a photoresist pattern with excellent etching resistance. [Brief explanation of the drawings]

[0038] [Figure 1] FIG. 1 is a schematic diagram showing a multilayer molecular film photoresist having a vertical molecular beam structure according to an embodiment of the present invention. [Figure 2] FIG. 2 is a schematic diagram showing a multilayer molecular film photoresist having a vertical molecular beam structure according to an embodiment of the present invention. [Figure 3] FIG. 3 is a schematic diagram showing an apparatus for manufacturing a multilayer molecular film photoresist having a vertical molecular beam structure according to an embodiment of the present invention. [Figure 4-7] 4 to 7 are schematic diagrams sequentially illustrating a photolithography method according to one embodiment of the present invention. [Figure 8]FIG. 8 shows a multilayer molecular film photoresist having a vertical molecular beam structure formed by this manufacturing example. [Figure 9] FIG. 9 is a graph showing the film formation rate as a function of the supply time of each precursor in producing the photoresist according to Production Example 1. [Figure 10] FIG. 10 is a graph showing the change in film thickness depending on the number of cycles of the photoresist according to Production Example 1, and an AFM image of the surface. [Figure 11] FIG. 11 is an SEM image taken after the photoresist obtained in Production Example 1 was patterned. [Figure 12] FIG. 12 is a schematic diagram showing cross-linking in the photoresist during the exposure process of FIG. [Figure 13] FIG. 13 is a graph showing the sensitivity of the photoresist obtained in Production Example 1 to an electron beam. [Figure 14-15] FIG. 14 is a schematic diagram showing the form and dose conditions for EUV irradiation, and FIG. 15 is an optical photograph of the photoresist pattern obtained after irradiating the photoresist of Production Example 1 with the EUV pattern shown in FIG. [Figure 16] FIG. 16 is a graph showing the change in film thickness depending on the number of cycles of the photoresist according to Production Example 2, and an AFM image of the surface. [Figure 17] FIG. 17 is a graph showing the change in film thickness depending on the number of cycles of the photoresist according to Production Example 3, and an AFM image of the surface. DETAILED DESCRIPTION OF THE INVENTION

[0039] In this specification, the term "metal" may be a concept that includes all metals, but as an example, it may be a transition metal, a post-transition metal, or a metalloid.

[0040] In this specification, the radiation may be, by way of example only, EUV or E-beam, but is not limited thereto in some cases.

[0041] As used herein, a single molecule refers to a molecule that is not a polymer, and may refer to, for example, a small molecule, specifically a molecule having 100 atoms or less, specifically a molecule having 30 atoms or less.

[0042] As used herein, when molecules or functional groups are "linked by a bond," this can mean that they are directly linked, or that they are indirectly linked via another molecule or functional group disposed between them.

[0043] In this specification, when it is stated that "number of carbon atoms (C)X to number of carbon atoms (C)Y" is used, it should be understood that it also describes cases where the number of carbon atoms is any integer between number of carbon atoms X and number of carbon atoms Y. For example, when it is stated as C1 to C10, it should be understood that C1, C2, C3, C4, C5, C6, C7, C8, C9, and C10 are all described.

[0044] In this specification, when "X to Y" is stated, it should be interpreted as including all integers between X and Y. For example, when "1 to 10" is stated, it should be interpreted as including all of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0045] In this specification, the term "aromatic ring" refers to an aromatic ring having 5 to 12 members, specifically 5 to 6 members, and may have a homocyclic structure in which all of the constituent members are carbon, or a heterocyclic structure in which some of the constituent members are substituted with heteroelements.

[0046] In this specification, the elements constituting the main chain of an "alkylene group" or an "alkyl group" may all be carbon, or some of the carbon may be substituted with O, S, N, C=O, or Si. The substituted elements are not limited to these.

[0047] FIG. 1 is a schematic diagram showing a multilayer molecular film photoresist having a vertical molecular beam structure according to an embodiment of the present invention.

[0048] Referring to FIG. 1 , a substrate 10 may be provided. The substrate may be a bare substrate, such as a semiconductor substrate, a glass substrate, or a flexible substrate. For example, the flexible substrate may be a polymer substrate. At least one element (not shown), such as a transistor, a memory, a diode, a solar cell, an optical element, a biosensor, a nanoelectromechanical system (NEMS), a microelectromechanical system (MEMS), a nanoelement, or a chemical sensor, may be formed on the substrate. The element may be an organic electronic element, such as an organic light-emitting diode (OLED) or an organic solar cell. Thus, in this embodiment, the substrate 10 may be a bare substrate or a bare substrate on which the element is formed.

[0049] A layer to be etched 20 may be formed on the substrate 10. The layer to be etched 20 is a layer that is etched using a photoresist pattern as an etching mask after a photoresist pattern is formed, and may be made of various materials used in semiconductor processes. For example, the layer to be etched 20 may be a metal film, a semiconductor film, an insulating film, or a composite film containing any of these. The metal film is used to form wiring and may be aluminum, tungsten, titanium, or a composite film containing any of these. The semiconductor film may be a silicon film, such as a single-crystal silicon, polysilicon, or amorphous silicon film, or a composite film containing any of these. The insulating film may be an inorganic insulating film such as a silicon oxide film or a silicon nitride film, an organic insulating film such as an amorphous carbon film, or a composite film containing any of these. For example, the layer to be etched 20 may be a bare substrate.

[0050] The layer to be etched 20 may have a surface functional group, for example, a hydroxyl group, a thiol group, an amine group, or a phosphine group, or may be surface-treated to have such a functional group.

[0051] A multilayer molecular film photoresist 30 having a molecular beam structure may be formed on the etching layer 20, specifically, a multilayer molecular film photoresist 30 including a plurality of molecular lines (ML) each extending above the substrate 10 and arranged laterally. In one example, the molecular lines (ML) may extend upward, for example, vertically relative to the substrate 10, and the lateral direction may be substantially parallel to the surface of the substrate 10.

[0052] Each molecular beam (ML) may include linearly linked monomolecules, each of which may include a plurality of main inorganic monomolecules (M1, M2, M3) containing a metal atom and an organic monomolecule (O1, O2, O3) interposed between at least some of the main inorganic monomolecules. Such a multilayer molecular film photoresist 30 may be referred to as an organic-inorganic multilayer molecular film photoresist. In this specification, a molecular beam (ML) may be defined as a backbone, molecular chain, or chain formed by the main inorganic monomolecules and the organic monomolecules linearly linked by bonds. The bonds may be covalent or coordinate bonds.

[0053] In one example, the organic monolayer may further include side inorganic monomolecules (not shown) positioned between the molecular beams (ML) and bonded to the sides O1, O2, and O3 of the organic monolayer. In this specification, "side" refers to the direction of extension of the molecular beams (ML), i.e., a direction intersecting the upward direction of the substrate, and may also refer to a lateral direction parallel to the substrate. The main inorganic monolayer, or the main inorganic monolayer and the organic monolayer, may be connected to another monolayer by a bond selected from the group consisting of -O-, -S-, -Se-, -NR- (R is H or CH3), and -PR- (R is H or CH3) contained in one of the adjacent monolayers. Furthermore, the organic monolayer and the inorganic monolayer on the side may be linked to the other monolayer by a bond selected from the group consisting of -O-, -S-, -Se-, -NR- (R is H or CH3), and -PR- (R is H or CH3) contained in one of the two monolayers. However, without being limited thereto, the monolayers may be linked indirectly by bonds via separate functional groups.

[0054] In this embodiment, since the multilayer molecular film photoresist 30 is formed using atomic layer deposition or molecular layer deposition, almost all of the molecular beams (MLs) may have substantially the same layer structure. In this case, the molecular beams (MLs) in the multilayer molecular film photoresist 30 may have substantially the same main inorganic monolayers and substantially the same organic monolayers in the lateral direction. That is, the main inorganic monolayers provided in the molecular beams may be arranged substantially identically in the lateral direction to form the main inorganic monolayer, and the organic monolayers provided in the molecular beams may be arranged substantially identically in the lateral direction to form the organic monolayer.

[0055] In addition, the molecular beams (ML) may be formed with a sufficiently narrow distance D between adjacent molecular beams (ML) so that van der Waals interactions (VI) occur between the organic monomolecules (O1, O2, O3) within adjacent molecular beams (ML). In this case, the van der Waals interactions (VI) may stabilize laterally adjacent molecular beams (ML) to prevent pattern collapse even in cases with a high aspect ratio, and may allow the molecular beams (ML) to extend in a substantially perpendicular direction to the substrate 10. In one example, the van der Waals interactions may be interactions between alkylene groups included in the organic monomolecules (O1, O2, O3) or π-π bonds between aromatic groups.

[0056] The molecular beam (ML) may include linearly linked monomolecules represented by the following Chemical Formula 1:

[0057] [ka]

[0058] In Formula 1, one of the *s may be a bond to a functional group in the lower layer or a functional group in the lower monolayer, and the other may be a bond to a functional group in the upper layer or a functional group in the upper monolayer. In this case, the bond may be, for example, a covalent bond. In Formula 1, m may be 0 to 10, n may be 1 to 10, and l may be 1 to 10,000, specifically 20 to 1,000, more specifically 25 to 100. Specifically, m may be 1 to 2, for example, m may be 1, and n may be 1 to 2, for example, n may be 1. OM is an organic monolayer, and MM is a main inorganic monolayer. This will be described in detail later. Formula 1 may refer to both a case where OM and MM are stacked on a lower layer in this order, as well as a case where MM and OM are stacked on a lower layer in this order.

[0059] In Figure 1, O1, O2, and O3 are all organic monolayers (OM), and may be different organic monolayers or the same organic monolayer. Also in Figure 1, M1, M2, and M3 are all main inorganic monolayers (MM), and may be different inorganic monolayers or the same inorganic monolayer. Also in Figure 1, n1, n2, and n3 are each independently the same as the value defined for n in Chemical Formula 1, m1, m2, and m3 are each independently the same as the value defined for m in Chemical Formula 1, and l1, l2, and l3 are each independently the same as the value defined for l in Chemical Formula 1.

[0060] In one example, the multilayer molecular film photoresist 30 may include at least one of a light-absorbing layer FL1, a photoreactive layer FL2, and an etching-resistant layer FL3, which are classified according to the primary function of the main inorganic monolayer, specifically, the primary function of the metal atom contained in the main inorganic monolayer. For example, the multilayer molecular film photoresist 30 may include one, two, or three of these layers. The stacking order of the light-absorbing layer FL1, the photoreactive layer FL2, and the etching-resistant layer FL3 may vary depending on the type of the etching target layer 20 and / or the type of pattern to be formed through photolithography. Meanwhile, the light-absorbing layer FL1, the photoreactive layer FL2, and the etching-resistant layer FL3 all essentially generate secondary electrons and undergo photoreactions due to light absorption.

[0061] FIG. 2 is a schematic diagram showing a multilayer molecular film photoresist having a vertical molecular beam structure according to an embodiment of the present invention.

[0062] 2, the molecular beam (ML) of the multilayer molecular film photoresist 30 includes a main inorganic monolayer and an organic monolayer linearly linked as represented by Chemical Formula 1, and some of the molecular beams (ML) include a main inorganic monolayer and an organic monolayer linearly linked as represented by Chemical Formula 2. In Fig. 2, l, m, and n in Chemical Formula 1 are all 1, MM is represented by MX or MY, and OM is represented by OX or OY. Some of the organic monolayers are laterally linked to side inorganic monolayers (MZ).

[0063] The main inorganic monolayer (MM, MX, or MY in Chemical Formula 1) may be a main inorganic monolayer containing a metal element, specifically an organic-inorganic monolayer. For example, the main inorganic monolayer may be a light-absorbing inorganic monolayer containing a metal element having a d orbital, a photoreactive inorganic monolayer containing Zr, Al, Hf, Zn, or In, or an etching-resistant inorganic monolayer containing Al, Ti, Cu, W, or Zn. The metal element having a d orbital, specifically a 4d or 5d orbital, may be, for example, Sn, Sb, Te, or Bi. Here, the classification of inorganic monolayers refers to their primary function, and all of the inorganic monolayers listed are capable of light absorption and photoreaction.

[0064] Specifically, the main inorganic monolayer (MM, MX, MY) is an organic / inorganic monolayer having at least two organic functional groups or ligands, and a linking group (X a ), specifically, O, S, Se, NR (R is H or CH3), or PR (R is H or CH3), may be bonded to the underlying or lower monolayer, specifically, the organic monolayer (OM). The main inorganic monolayer (MM, MX, MY) may be an organic-inorganic monolayer represented by the following chemical formula 2:

[0065] [ka]

[0066] In Formula 2, one of the *'s may be a bond to a functional group or a lower monomolecule in a lower layer within the same molecular beam, specifically a functional group in a lower organic monomolecule, and the other may be a bond to a functional group or an upper monomolecule in an upper layer within the same molecular beam, specifically a functional group in an upper organic monomolecule. In this case, the bond may be, for example, a covalent bond. Z1 and Z2 may each independently be a direct bond, a C1 to C20 substituted or unsubstituted linear or branched alkylene group, a C1 to C20 substituted or unsubstituted linear or branched alkylene oxide, a C1 to C20 substituted or unsubstituted linear or branched alkyleneamino, a C1 to C20 substituted or unsubstituted linear or branched alkylenesilylamino, a C1 to C20 substituted or unsubstituted linear or branched alkylenethio, a C1 to C20 substituted or unsubstituted linear or branched alkyleneseleno, or a C1 to C20 substituted or unsubstituted linear or branched alkylenephosphino. 0 X may be a light-absorbing metal atom having a d orbital, a photoreactive metal atom such as Zr, Al, Hf, Zn, or In, or an etching-resistant metal atom such as Al, Ti, Cu, W, or Zn. The metal element having a d orbital, specifically a 4d or 5d orbital, may be, for example, Sn, Sb, Te, or Bi. a may be O, S, Se, NR (where R is H or CH3), or PR (where R is H or CH3).

[0067] L a and Lb is M 0 The sum of the numbers of these functional groups, na and nb, may be the maximum coordination number resulting from M0 minus the number of bonds with the upper and lower functional groups (Z1 and Z2), i.e., 2, or may be smaller than this. 0 For example, the sum of na and nb may be an integer between 0 and 4. a and L bmay be, independently of one another, a halogen group (e.g., Cl, Br, or I), a C1-C5 alkyl group, a C1-C5 alkylsilylamino group, a C1-C5 alkoxy group, a C1-C5 alkylthio group, a C1-C5 alkylseleno group, a C1-C5 alkylamino group, or a C1-C5 alkylphosphino group. Here, the C1-C5 alkyl group may be a substituted or unsubstituted linear or branched alkyl group. In addition, when na and / or nb in the above Chemical Formula 3 are 2 or more, L a and / or L b may be independently selected from the above examples. In one example, when the sum of na and nb is 2 or more, L a and L b Two of Z1, Z2, L may be taken together with the M0 to which they are attached to form a heterocyclyl or heteroaryl. a , or L b and M 0 Each bond between may be a covalent bond or a coordinate bond, independently of the other.

[0068] In Figure 2, M X and M Y is M in the above chemical formula 2 0 The main inorganic monolayer (MX) is exemplified by a case where na and nb are 0 and Z1 and Z2 are direct bonds, and the main inorganic monolayer (MY) is exemplified by a case where na and nb are both 1 and Z1 and Z2 are direct bonds.

[0069] The inorganic monolayer (MZ) on the side is represented by the following chemical formula 3.

[0070] [ka]

[0071] In the above Chemical Formula 3, X C may be O, S, Se, NR (where R is H or CH), or PR (where R is H or CH). In one example, X C may be S. R b2may be a halogen group (e.g., Cl, Br, or I), a C1-C5 alkyl group, a C1-C5 alkylsilylamino group, a C1-C5 alkoxy group, a C1-C5 alkylthio group, a C1-C5 alkylseleno group, a C1-C5 alkylamino group, or a C1-C5 alkylphosphino group. a , L b , na, nb, and M 0 is as defined in Formula 2. In some cases, R b2 , L a , and L b Two of them are directly or indirectly linked to M 0 and may combine to form a heterocyclyl or heteroaryl. b2 is M 0 In FIG. 2, in the inorganic monolayer (MZ) at the side, M Z is M in the above Chemical Formula 3 0 This corresponds to the case where na and nb are both 0 and Z1 and Z2 are all direct bonds.

[0072] In FIG. 2, Z1, Z2, and L of the main inorganic molecule (MX) bonded to the top of the organic molecule (OX) a , L b , na, nb, and M 0 are the Z1, Z2, L of the inorganic monolayer (MZ) bonded to the side of the organic monolayer (OX). a , L b , n a , n b , and M may be the same, which may be because the main inorganic monolayer (MX) bonded to the top of the organic monolayer (OX) and the side inorganic monolayer (MZ) bonded to the side of the organic monolayer (OX) are formed in the same step using the same metal precursor.

[0073] The organic monolayer (OM in Chemical Formula 1, OX and OY in FIG. 2) may have a linear chain having 2 to 7 carbon atoms or a non-aromatic or aromatic ring having 3 to 18 carbon atoms as a skeleton. A portion of the carbon atoms may be substituted with an element selected from the group consisting of C=O, N, S, O, and Si. The linear chain may extend in substantially the same direction as the extension direction of the molecular beam (ML). The long axis of the ring may be in substantially the same direction as the extension direction of the molecular beam (ML). The organic monolayer (OM in Chemical Formula 1, OX and OY in FIG. 2) may have a linking functional group (X) directly or indirectly bonded to the lower part of the skeleton. b ), specifically, -O-, -S-, -Se-, -NR- (where R is H or CH3), or -PR- (where R is H or CH3), may be bonded to the underlayer, specifically, the lower main inorganic monolayer.

[0074] In one example, a portion of the organic monolayer (OM in Chemical Formula 1, OX in FIG. 2) may have an amide group or an amine group in the linear chain or ring. When a side inorganic monolayer (MZ in Chemical Formula 2, x is 1 or more) is bonded to the organic monolayer, the amide group or amine group serves as a linking functional group (Xc) as -NR- (R is H or CH3), and a metal atom (M Z In another example, the organic single molecule (OM in Chemical Formula 1, OX in FIG. 2) may have a crosslinkable functional group (-ZX) attached to the side of the backbone. C R a3 , Z5 in Figure 2 is a direct bond) or a side inorganic monomolecule (MZ, -Z5X C M Z R b2 In FIG. 2, Z5 may be a direct bond. In this case, the linking functional group (X c ) may be O, S, Se, NR (R is H or CH3), or PR (R is H or CH3).

[0075] For example, OM in Chemical Formula 1 and OX and OY in FIG. 2 may be an organic monomolecule represented by Chemical Formula 4 below.

[0076] [ka]

[0077] In the formula 4, one of the *'s may be a bond with a functional group in a lower layer in the molecular beam or a functional group in a lower monomolecule (for example, a lower main inorganic monomolecule), and the other may be a bond with a functional group in an upper layer in the molecular beam or a functional group in an upper monomolecule (for example, an upper main inorganic monomolecule). In this case, the bond may be, for example, a covalent bond. X b may be O, S, Se, NR (where R is H or CH), or PR (where R is H or CH). In one example, X b is X a or X C and may be, for example, O or S. Z3 and Z4 may each independently be a direct bond or a C1-C5 linear or branched alkylene group. Here, the substitution may involve replacing hydrogen atoms of the alkylene group with various functional groups, for example, OH, SH, SeH, NR2 (where R is independently H or CH3), or PR2 (where R is independently H or CH3).

[0078] In one example, MR in Chemical Formula 4 may have a linear chain having 2 to 7 carbon atoms or a non-aromatic or aromatic ring having 3 to 18 carbon atoms as a skeleton. Some of the carbon atoms may be substituted with an element selected from the group consisting of C=O, N, S, O, and Si. The linear chain may be, for example, a linear alkylene group having C3 to C7 atoms, specifically, C3 to C5 atoms. The linear chain may be substituted with an alkyl group having C1 to C2 atoms. When MR is a linear chain, Z3 and Z4 may be direct bonds.

[0079] In one example, at least some of the MR of the organic monomolecules may be -(Z5X C R a3 ) x Here, Z5 may be a direct bond or a C1 to C5, specifically a C1 to C3, substituted or unsubstituted, linear or branched alkylene group. X Cmay be O, S, Se, NR (where R is H or CH), or PR (where R is H or CH). In one example, X C may be S. R a3 may be hydrogen or a C1-C2 alkyl group. In one example, Z5 may be a direct bond, in which case X may be C may be directly bonded. X may be 1 to 2. The side functional group -Z5X C R a3 may be bonded to carbon or N or Si contained in MR by substituting a carbon. C R a3 When -(ZX) is attached to the same member of MR, the number of such members (x) may be limited to the number of covalent bonds that can be made to the member. C R a3 ) x In the above formula, x is 1 and Z5 is a direct bond. In another example, the MR may have an amide group or an amine group in the chain.

[0080] In addition, a side inorganic monomolecule (MZ) represented by Chemical Formula 4 may be bonded to at least a part of the organic monomolecules MR.

[0081] In FIG. 2, OX indicates the first layer (FL X ) is an organic monomolecular molecule provided within the crosslinkable functional group (-(ZX c R a3 ) x , x=1, Z5 represents a direct bond) or an organic monolayer bonded to a lateral inorganic monolayer (MZ), and OY represents a second layer (FL Y ) and the crosslinkable functional group or the inorganic monomer on the side is not bonded thereto.

[0082] The multilayer molecular film photoresist 30 may have a structure in which main inorganic molecules (MM) and organic molecules (OM) are alternately laminated, and in this case, the organic molecules (OM) may be arranged between the main inorganic molecules (MM), and the main inorganic molecules (MM) and the organic molecules (OM) may be self-assembled. As a result, the molecular beams (ML) may extend in a direction vertical to the substrate 10, for example, in an upward direction, while being spaced apart from each other.

[0083] The van der Waals interaction (VI) between organic monomolecules (OM) in adjacent molecular beams (ML) stabilizes the laterally adjacent molecular beams (ML) and prevents pattern collapse even in cases where the pattern has a high aspect ratio.

[0084] FIG. 3 is a schematic diagram showing an apparatus for manufacturing a multilayer molecular film photoresist having a vertical molecular beam structure according to an embodiment of the present invention.

[0085] 2 and 3, a substrate (S) can be loaded onto a stage 102 in a chamber 100 having a gas inlet 120 and a gas outlet 140. The substrate (S) may be the substrate 10 on which the etching layer 20 described with reference to FIG.

[0086] Before loading the substrate (S), the chamber 100 may be heated to and maintained at a deposition temperature by the control unit 150. The deposition temperature may be 20 to 250°C, 50 to 200°C, 80 to 150°C, 90 to 140°C, or 100 to 130°C. The gas outlet 140 may be connected to a vacuum pump.

[0087] First, all gas inlet valves 130, 132, and 134 connected to the gas inlet 120 are closed, and the gas outlet valve 142 connected to the gas outlet 140 is opened to evacuate the inside of the chamber 100.

[0088] The multilayer molecular film photoresist 30 can then be formed by performing a cycle including a step of forming a main inorganic monolayer (MM in Chemical Formula 1, specifically, MX or MY in FIG. 2) and a step of forming an organic monolayer (OM in Chemical Formula 1, specifically, OX or OY in FIG. 2). The steps of forming the inorganic monolayer and the organic monolayer can be performed using atomic layer deposition, specifically, molecular layer deposition. Although the present specification describes a unit cycle in which an organic monolayer is formed and then an inorganic monolayer is formed, this concept also includes forming an inorganic monolayer and then an organic monolayer when performing this unit cycle.

[0089] In the step of forming the organic monolayer (OM of Chemical Formula 1, specifically, OX or OY of FIG. 4), an organic monolayer unit cycle can be performed, which includes an organic precursor dosing step in which an organic precursor is dosed and chemically bonded to the underlayer in a self-assembly manner, and a purge step in which a purge gas is supplied to purge unreacted organic precursors and reaction products.

[0090] The organic precursor has a skeleton of a linear chain having 2 to 7 carbons or a non-aromatic or aromatic ring having 3 to 18 carbons, each carbon being selected from the group consisting of C, C=O, N, S, O, and Si. OR bonded directly or indirectly to one side of the skeleton. a1 , S.R. a1 , SeR a1 , NRR a1 (R is H or CH3) or PRR a1 (R is H or CH3), and OR is directly or indirectly bonded to the other side. a2 , S.R. a2 , SeR a2 , NRR a2 (R is H or CH3) or PRR a2 (R may have H or CH3). a1 and R a2may be independently hydrogen or a C1-C2 alkyl group. In addition, the organic precursor may have an amide group or an amine group in the linear chain or ring. In another example, OR may be attached to the side of the linear chain, which is the backbone. a3 , S.R. a3 , SeR a3 , NRR a3 (R is H or CH3) or PRR a3 (R is H or CH3). a3 may be hydrogen or a C1-C2 alkyl group.

[0091] In one example, the organic precursor is represented by the following chemical formula 5:

[0092] [ka]

[0093] In the above formula 5, R a1 and R a2 may each independently be hydrogen or a C1-C2 alkyl group, and X b and X a may be, independently of each other, O, S, Se, NR (where R is H or CH3), or PR (where R is H or CH3). b is O and X a may be S. Z3, Z4, and MR are as defined in Chemical Formula 5 above.

[0094] -(Z5X C R a3 ) x is a crosslinkable functional group, and Z5 may be a direct bond or a C1 to C5, specifically a C1 to C3, substituted or unsubstituted, linear or branched alkylene group. X C may be O, S, Se, NR (where R is H or CH), or PR (where R is H or CH). In one example, X C may be S. R a3may be hydrogen or a C1-C2 alkyl group. In one example, Z5 may be a direct bond, in which case X may be C may be directly bonded. x may be 0 to 2. When x is 1 or 2, the crosslinkable functional group -Z5X C R a3 may be bonded to carbon in MR, specifically C, N, or Si. C R a3 When n is 0 in the above Chemical Formula 2, the MR may have an amide group or an amine group in the chain. In another example, when n is 0 in the above Chemical Formula 2, the MR may consist of only carbon. In FIG. 2, -(ZX C R a3 ) x In the above formula, x is 1 and Z5 is a direct bond.

[0095] In Formula 5, when x is 1 or 0 and MR has an amide group or an amine group as a reactive functional group, examples of the organic precursor are as follows:

[0096] [ka]

[0097] In the above Chemical Formula 5, when x is 0 and MR does not have an amide group or an amine group as a reactive functional group, examples of the organic precursor are as follows:

[0098] [ka]

[0099] In the above, n may be 1 or 2.

[0100] In the organic precursor dosing step, a reaction according to the following reaction formula 1 may occur.

[0101] [ka]

[0102] In the above reaction formula 1, R represents a functional group on the surface of the lower layer or a lower monolayer, specifically, a surface functional group of the lower main inorganic monolayer (R b2 ), and R0 may be hydrogen, a hydroxy group, a thiol group, an amine group, a phosphine group, a C1-C5 alkyl group, a C1-C5 alkoxy group, a C1-C5 alkylthio group, a C1-C5 alkylseleno group, a C1-C5 alkylamine group, or a C1-C5 alkylphospino group. R a1 X b -Z3-MR(-Z5-X C R a3 ) x (-Z4-X a R a2 ) is an organic precursor, and each functional group is as defined in Chemical Formula 5. b and X a When X are different from each other, the functional group with higher reactivity may be bonded to the functional group on the surface of the underlying layer. b and X a When X is O and S, respectively, O may be bonded to a functional group on the surface of the underlying layer. C X also bonds with the functional groups on the underlying surface. b It may also be a functional group that is less reactive with, for example, S.

[0103] Referring to Reaction Scheme 1, the organic precursor may react with functional groups on the surface of the underlayer to self-assemble onto the underlayer. a1 may be produced as a reaction by-product. Thereafter, the remaining excess organic precursor and the reaction by-product may be purged in a purge step.

[0104] In the organic precursor dosing step, the organic precursor may be supplied from the organic precursor storage unit 114 into the chamber 100 with the organic precursor control valve 134 open and the gas exhaust valve 142 closed (organic precursor supply step). The organic precursor may be stored in the organic precursor storage unit 114 in a solid, liquid, or gaseous state. The organic precursor storage unit 114 may be heated, and the organic precursor may be supplied into the chamber 100 at a predetermined vapor pressure. In one embodiment, the supplied organic precursor may be supplied without a carrier gas. That is, the organic precursor may be supplied alone into the chamber 100.

[0105] Since the organic precursor is supplied with the gas exhaust valve 142 closed, it accumulates in the chamber 100, increasing the pressure within the chamber 100. The organic precursor may be supplied until the pressure within the chamber 100 reaches a reaction pressure (organic precursor supply step). The reaction pressure is the pressure of the organic precursor alone within the chamber 100, and may be in the range of 10 mTorr to 10 Torr, specifically, 50 mTorr to 10 Torr, 100 mTorr to 6 Torr, 130 mTorr to 3 Torr, or 150 mTorr to 1 Torr. Generally, the precursor is dosed into the chamber together with a carrier gas. In this case, considering that the partial pressure of the precursor is approximately 1 to 10 mTorr, a pressure of the organic precursor alone within the chamber 100 of 50 mTorr or more may indicate that the organic precursor is pressurized.

[0106] When the reaction pressure is reached, the organic precursor control valve 134 is closed, and the chamber can be sealed for a predetermined time with the gas exhaust valve 142 closed (organic precursor exposure step). The organic precursor supply step and the organic precursor exposure step are sometimes referred to as an organic precursor dosing step. However, the organic precursor exposure step may be omitted in some cases. In the organic precursor dosing step, the reaction according to Reaction Scheme 1 may occur.

[0107] Thereafter, the chamber 100 can be purged (organic precursor purging step). Specifically, the purge gas control valve 132 and the gas exhaust valve 142 can be opened to allow the purge gas in the purge gas reservoir 112 to flow onto the surface of the substrate to remove excess unreacted organic precursor and the reaction by-products. In this case, the purge gas is an inert gas, and the inert gas may include, for example, argon (Ar), nitrogen (N), or a combination thereof.

[0108] In the step of forming the inorganic monomolecule (MM in Chemical Formula 1, specifically, MX or MY in FIG. 4), a unit cycle may be performed that includes an inorganic precursor dosing step in which an inorganic precursor is dosed and chemically bonded to a lower layer in a self-assembly manner, and a purge step in which a purge gas is supplied to purge unreacted inorganic precursors and reaction products.

[0109] The inorganic precursor may be an organic / inorganic monolayer having at least two organic functional groups or ligands, and is represented by the following chemical formula 6:

[0110] [ka]

[0111] In the above formula 6, R b1 and R b2 may be, independently of one another, a halogen group (e.g., Cl, Br, or I), a C1-C5 alkyl group, a C1-C5 alkylsilylamino group, a C1-C5 alkoxy group, a C1-C5 alkylthio group, a C1-C5 alkylseleno group, a C1-C5 alkylamino group, or a C1-C5 alkylphosphino group. Here, the C1-C5 alkyl group may be a substituted or unsubstituted linear or branched alkyl group. Z1, Z2, and L a , L b , n a , n b , and M 0 is as defined in Formula 2. In addition, in some cases, R b1, R b2 , L a , and L b Two of them are directly or indirectly linked to M 0 and may combine to form a heterocyclyl or heteroaryl. b1 and R b2 At least one of the 0 It may be in a coordinate bond with

[0112] In one example, Z1 and Z2 are bonds and L a , L b , R b1 and R b2 In another example, Z and Z are bonds and L a and L b are the same functional groups, and R b1 and R b2 is the same functional group, but L a and R b1 may be different functional groups. Examples of the inorganic precursor are as follows:

[0113] [ka] JPEG2026506378000019.jpg161128JPEG2026506378000020.jpg101128

[0114] In the metal precursor, dmap means 1-dimethylamino-2-methyl-2-propoxy, and R1, R2, R3, and R4 may each independently be a C1 to C5 alkyl group.

[0115] In the inorganic precursor dosing step, the inorganic precursor gas may be supplied from the inorganic precursor storage unit 110 into the chamber 100 with the inorganic precursor gas control valve 130 open and the gas exhaust valve 142 closed (inorganic precursor supply step). The inorganic precursor may be stored in the inorganic precursor storage unit 110 in a solid, liquid, or gaseous state. The inorganic precursor storage unit 110 may be heated to a temperature below the thermal decomposition temperature of the inorganic precursor, thereby supplying the inorganic precursor into the chamber 100 at a predetermined vapor pressure. At this time, the inorganic precursor may be supplied without a carrier gas. That is, the inorganic precursor may be supplied alone to the chamber 100.

[0116] Since the inorganic precursor is supplied with the gas exhaust valve 142 closed, it accumulates in the chamber 100, increasing the pressure within the chamber 100. The indium precursor may be supplied until the pressure within the chamber 100 reaches a reaction pressure (inorganic precursor supply step). At this time, the reaction pressure may be a pressure of the inorganic precursor alone within the chamber 100 in the range of 10 mTorr to 10 Torr, specifically, 50 mTorr to 10 Torr, 100 mTorr to 6 Torr, 600 mTorr to 5 Torr, or 700 mTorr to 2 Torr. Typically, the precursor is dosed into the chamber together with a carrier gas. In this case, considering that the precursor partial pressure is approximately 1 mTorr, a pressure of the inorganic precursor alone within the chamber 100 of 50 mTorr or more may indicate that the inorganic precursor is pressurized.

[0117] When the reaction pressure is reached, the inorganic precursor gas control valve 130 is closed, and the chamber can be sealed for a predetermined time (inorganic precursor exposure step). The inorganic precursor supply step and the inorganic precursor exposure step are sometimes referred to as the inorganic precursor dosing step. However, the inorganic precursor exposure step may be omitted in some cases. In the inorganic precursor dosing step, the reaction according to Reaction 2, and in some cases, both Reaction 2 and Reaction 3, may occur.

[0118] Thereafter, the chamber 100 can be purged (inorganic precursor purging step). Specifically, the purge gas control valve 132 and the gas exhaust valve 142 can be opened to allow the purge gas in the purge gas reservoir 112 to flow over the surface of the substrate in the chamber, thereby removing excess inorganic precursor gas and the reaction by-products that could not be adsorbed onto the surface of the substrate. In this case, the purge gas is an inert gas, and the inert gas may include, for example, argon (Ar), nitrogen (N), or a combination thereof.

[0119] In one example of the inorganic precursor dosing step, a reaction according to the following reaction formula 2 may occur:

[0120] [ka]

[0121] In the reaction formula 2, *-X a R a2 is the surface functional group of the underlying layer, specifically, the surface functional group of the previously formed organic monolayer (OM), and the inorganic precursor of Formula 6 may react with the surface functional group of the previously formed organic monolayer (OM) to self-assemble on the surface of the organic monolayer (OM). In this process, R a2 R b1 may be generated as a reaction by-product. Subsequently, in a purging step, the remaining inorganic precursor and the reaction by-product may be purged. In Reaction Scheme 2, each functional group may be the same as defined in Reaction Scheme 1 and Chemical Formula 6.

[0122] In another example of the inorganic precursor dosing step, a reaction according to the following reaction formula 3 may occur in addition to the reaction formula 2. This is because the organic precursor used in the step of forming the organic molecular layer (OM) has a crosslinkable functional group, -Z5X, at the side. C R a3 That is, in Chemical Formula 5, x is 1 or more.

[0123] [ka]

[0124] In the reaction formula 3, *-X C R a3 is a functional group located on the side of the organic monolayer (OM) formed previously, i.e., a crosslinkable functional group, and the inorganic precursor of Formula 6 supplied in the inorganic precursor dosing step may react with the crosslinkable functional group to be positioned between the organic monolayer (OM). In this process, R a3 R b1 may be generated as a reaction by-product. Then, in a purge step, the remaining inorganic precursor and the reaction by-products of Reactions 2 and 3 (RaR b1 and R a3 R b1 In Reaction Scheme 3, each functional group may be the same as those defined in Chemical Formula 5 and Chemical Formula 6.

[0125] However, the present invention is not limited thereto. When the organic precursor used in the step of forming the organic molecular layer (OM) contains an amide group or an amine group in the chain of the alkylene group serving as the skeleton, X c is N and R a3 is hydrogen or a C1-C2 alkyl group, specifically, -X c R a3 is -NH- or -NR a3 - may be.

[0126] As an example, the organic precursor used to form the FLx layer in FIG. 2 contains a crosslinkable functional group, -Z5X C R a3 In the inorganic precursor dosing step, the reactions of Reaction Scheme 2 and Reaction Scheme 3 can occur simultaneously. As a result, the inorganic precursor reacts with the top of the organic monolayer (OX) in the FLx layer (Reaction Scheme 2), bonding the main inorganic monolayer (MX), and the crosslinkable functional group -Z5X is attached to a part of the organic monolayer (OX). C R a3The inorganic precursor may be reacted with the inorganic monolayer (MZ) to bond the inorganic monolayer (MZ) to the organic monolayer (OX) by the reaction (Reaction Scheme 3), and the organic monolayer (OX) may be joined to the inorganic monolayer (MZ) by the crosslinkable functional group -ZX. c R a3 may remain unreacted with the inorganic precursor. In this case, M O is MX, and in reaction 3, M O is shown in FIG. 2 as MZ. X Although shown without La and Lb ligands, this is not limited to M X na La and nb Lb may be bonded to Z. In addition, in the above chemical formulas and reaction formulas, Z1, Z2, Z3, Z4, and Z5 are shown in Figure 2 as being bonded, but the present invention is not limited to this.

[0127] On the other hand, FL Y The organic monolayer (OY) in the layer is an organic monolayer formed by proceeding with Reaction Scheme 1 (x is 0) using an organic precursor that does not contain a crosslinkable functional group, specifically, an organic precursor that does not have a reactive functional group in the backbone (MR) where x is 0 in Chemical Formula 5, and only the reaction of Reaction Scheme 2 can occur when forming the inorganic monolayer (MY). In the drawings, both na and nb are shown to be 1 in Chemical Formula 6 and Reaction Scheme 2, but the present invention is not limited to this.

[0128] Also, in Figure 2, FL x Layers and FL Y Although the present invention is not limited to the above, the present invention can also be applied to the formation of both layers. x When forming the organic monolayer (OY), only the FL x Unlike the main inorganic monolayer (MX) in the layer, the inorganic monolayer (MZ) on the side cannot participate in the reaction with the dosing organic precursor due to insufficient space. Z -R bonded to b2 This may be a FL x The same applies to the case where only layers are formed continuously.

[0129] The control unit 150 may control the opening and closing of the valve and the temperature of the chamber.

[0130] Thus, the reaction shown in Reaction Scheme 1 may be performed in a pressurized environment where the pressure of the organic precursor alone is 50 mTorr or more, specifically 100 mTorr or more. In this case, the organic precursor may react densely on the substrate, and the organic precursor chains may be arranged upward, for example, vertically, relative to the substrate 10. Furthermore, the reaction shown in Reaction Scheme 1 may proceed with the gas exhaust valve 142 closed, i.e., specifically, in a pressurized stagnant environment rather than a laminar flow environment. In this case, the organic precursor may react densely on the substrate more efficiently. However, the present invention is not limited thereto, and the organic precursor may be supplied alone without a carrier gas with the gas exhaust valve 142 open, forming a laminar flow within the chamber.

[0131] A molecular layer deposition apparatus according to an embodiment of the present invention can perform a cycle including a step of forming a primary inorganic monolayer (MM in Chemical Formula 1) and a step of forming an organic molecular layer (OM in Chemical Formula 1) multiple times, specifically, the number of times indicated by 1 in Chemical Formula 1.

[0132] When the first primary inorganic monolayer (MX) or the second primary inorganic monolayer (MY) is formed of multiple primary inorganic monolayers (i.e., n is 2 or greater in Chemical Formula 1), a unit cycle can be repeated, including a step of dosing an inorganic precursor according to Reaction Formula 2 (or both Reaction Formulas 2 and 3) and a step of purging, followed by a step of dosing a reactive gas to react with the inorganic precursor chemically bonded to the lower layer, and a step of purging unreacted reactive gas and reaction products by supplying a purge gas. The reactive gas may be hydrogen, an oxygen-containing gas (e.g., O, O, HO), a nitrogen-containing gas (e.g., NH), etc.

[0133] 2 and 4 to 7 are schematic diagrams sequentially illustrating a photolithography method according to one embodiment of the present invention.

[0134] As described with reference to FIG. 2, a multilayer molecular photoresist 30 may be formed.

[0135] 4, a portion of the multilayer molecular film photoresist 30 may be irradiated with radiation (hv), specifically, EUV or E-beam. In this case, EUV may be radiation having a wavelength of 13.5 nm. In this case, the main inorganic monolayers, for example, the first main inorganic monolayer (MX), the second main inorganic monolayer (MY), and the metal atoms M in the side inorganic monolayers (MZ), may be irradiated with radiation (hv). X , M Y , or M Z can absorb the radiation and generate secondary electrons.

[0136] The secondary electrons may form cross-links between adjacent molecular beams (ML). Specifically, the unreacted functional groups -R of the side inorganic monomolecules (MZ) may be cross-linked. b2 represents the remaining crosslinkable functional group (-X) of the first organic monomer (OX). c R a3 ) reacts with R b2 R a3 as a reaction by-product, and the organic atoms (M Z ) and the backbone MR of the first organic monolayer (OX) c -Can form bonds.

[0137] In addition, the first main inorganic monomolecule (MX) corresponds to the case where na and nb are both 0 in chemical formula 2, and in this case, M X is the X of other adjacent molecular beams. a and / or X b The second main inorganic monolayer (MY) corresponds to the case where na and nb are both 1 in the chemical formula 3, and in this case, the M provided in the adjacent molecular beam Y -L a and L b -M Y is MY -YM Y wherein Y can be O, S, Se, N, or P.

[0138] Such an M Y -YM Y Combine, M X and X a and / or X b The bond between, and M Z -X c The -MR bond, as a crosslinked bond due to exposure, may not be etched by a developer, such as a developing gas or developing plasma, that develops the multilayer molecular film photoresist pattern formed by exposure.

[0139] 5, the multilayer molecular film photoresist 30 exposed to radiation may be exposed to a developer. In this case, the multilayer molecular film photoresist 30 may be removed by the developer except for the portions where cross-links are formed between adjacent molecular beams (ML), thereby forming a multilayer molecular film photoresist pattern 31. The developer may be a developing solution such as water, isopropyl alcohol (IPA), methyl isobutyl ketone (MIBK), or tetramethylammonium hydroxide (TMAH), or a developing gas such as CF4, Ar, O2, or CHF3, or a plasma generated therefrom.

[0140] 6, the film to be etched 20 may be etched using the multilayer molecular film photoresist pattern 31 as a mask. This etching may be plasma etching, for example.

[0141] 7, the multilayer molecular film photoresist pattern 31 may be removed, which may be done by ashing.

[0142] As described above, the multilayer molecular film photoresist 30 can grow above the substrate without entanglement or tilting due to the self-organization of inorganic and organic monomolecules linked by bonds within the molecular beam. Furthermore, the molecular beams may be uniformly arranged laterally. The molecular beams may be densely formed so that van der Waals interactions (VI) may exist between organic monomolecules within adjacent molecular beams. The van der Waals interactions may stabilize laterally adjacent molecular beams, preventing pattern collapse even in cases with a high aspect ratio. The dense formation of the molecular beams may be due to the dosing of the organic and / or inorganic precursors without the use of a carrier gas and the increased pressure of the organic and / or inorganic precursors within the chamber. For this purpose, the dosing of the organic and / or inorganic precursors may be performed with the gas exhaust port of the chamber closed. In this case, the height of the unit layer may be approximately the same as the length of the unit layer, which reflects the actual size of the atoms within the unit layer and the actual length of the bonds between the atoms.

[0143] In this way, the spacing between molecular beams (D in FIG. 1 or FIG. 2) is very small, less than 1 nm, specifically less than 0.5 nm. Furthermore, by separating molecular beams rather than particles during exposure and development, the line edge roughness (LER), which refers to the side roughness of a pattern, can be significantly reduced. For example, a very low line edge roughness of 1.2 nm or less can be achieved. Resolution can also be significantly reduced. For example, a resolution of 6 nm or less can be achieved. Additionally, the multilayer molecular film photoresist 30 includes inorganic atoms with very high light absorption rate against EUV, specifically, light-absorbing inorganic monomolecules with metal atoms having 4d or 5d orbitals, and has low stochastic failure and high photosensitivity (e.g., 10 mJ / cm ) even against EUV, which has a low photon density. 2 ) can be shown.

[0144] In addition, when the backbone (MR in Chemical Formula 5) of the organic precursor or organic monolayer is a linear chain or a non-aromatic ring, the organic monolayer in the molecular beam can form a tight molecular beam through van der Waals bonds. In addition, among the carbons constituting the backbone (MR) in Chemical Formula 5, carbons excluding the α carbons adjacent to Z3 and Z5 can be bonded with a crosslinkable functional group -Z5X. C R a3 When the inorganic precursor is directly or indirectly bonded to the molecular beam and placed between the molecular beams, the spacing between the organic monomolecules can be adjusted so as not to be too narrow. C R a3 The inorganic precursor can be introduced and reacted with the molecular beam, and as a result, the inorganic monomolecules can be placed between the molecular beams and the inorganic monomolecules on the sides can be bonded. On the other hand, the inorganic monomolecules on the sides may not react with the organic precursor in the subsequent organic precursor dosing step because there is not enough space for the organic precursor to be introduced, and the unreacted functional groups (R a3 The unreacted functional group (Ra3) at the end of the side inorganic monomer further reacts with the organic monomer upon irradiation and is crosslinked, thereby forming a photoresist pattern with excellent etching resistance.

[0145] In the following, preferred examples are presented to aid in understanding the present invention, but the following examples are provided to aid in understanding the present invention and are not intended to limit the scope of the present invention.

[0146] Manufacturing Example 1: Photoresist Manufacturing Example 1 FIG. 8 shows a multilayer molecular film photoresist having a vertical molecular beam structure formed by this manufacturing example.

[0147] Referring to FIG. 8, a substrate was loaded into a chamber equipped with a gas inlet and a gas outlet, and the substrate temperature was heated to 100°C. With the gas outlet closed, DMP (2,3-dimercaptopropanol) was supplied onto the substrate as an organic precursor without a carrier gas through the gas inlet until the chamber pressure reached 200 mTorr (organic precursor supply step). The chamber inlet was then closed, and the chamber pressure was maintained at 200 mTorr. The organic precursor was then reacted on the substrate for 1 second (organic precursor exposure step). Then, with both the gas inlet and gas outlet open, argon purge gas was supplied into the gas inlet for 600 seconds to purge reaction by-products and residual reaction gas (organic precursor purge step). The organic precursor supply step, organic precursor exposure step, and organic precursor purge step constitute an organic precursor subcycle.

[0148] Then, with the gas outlet closed, DEZ (diethyl zinc), an inorganic precursor, was supplied onto the organic precursor layer through the gas inlet without a carrier gas until the pressure inside the chamber reached 1 Torr (inorganic precursor supply step). Then, with the chamber inlet also closed and the chamber pressure maintained at 1 Torr, the Zn precursor was reacted on the surface of the organic precursor layer for 1 second (inorganic precursor exposure step). Then, with both the gas inlet and gas outlet open, argon, a purge gas, was supplied into the gas inlet for 200 seconds to purge reaction by-products and residual reaction gas (inorganic precursor purge step). The inorganic precursor supply step, inorganic precursor exposure step, and inorganic precursor purge step constitute an inorganic precursor subcycle.

[0149] A unit cycle consisting of one inorganic precursor subcycle and one organic precursor subcycle was repeated 33 times to form a multilayer molecular film photoresist having a thickness of approximately 20 nm.

[0150] Manufacturing Example 2: Photoresist Manufacturing Example 2 The same organic precursor subcycle as in Preparation Example 1 was carried out. Then, with the gas outlet closed, the inorganic precursor, Hf precursor (TDMA)Hf (tetrakisdimethylamido hafnium), was supplied onto the organic precursor layer through the gas inlet without carrier gas until the pressure inside the chamber reached 750 mTorr (inorganic precursor supply step). The chamber inlet was then closed, and the chamber pressure was maintained at 750 mTorr. The Hf precursor was reacted on the surface of the organic precursor layer for 1 second (inorganic precursor exposure step). Then, with both the gas inlet and gas outlet open, argon purge gas was supplied into the gas inlet for 300 seconds to purge reaction by-products and residual reaction gas (inorganic precursor purge step). The inorganic precursor supply step, inorganic precursor exposure step, and inorganic precursor purge step constitute the inorganic precursor subcycle.

[0151] A unit cycle consisting of one inorganic precursor subcycle and one organic precursor subcycle was repeated 31 times to form a multilayer molecular film photoresist having a thickness of about 20 nm.

[0152] Manufacturing Example 3: Photoresist Manufacturing Example 3 An organic precursor subcycle similar to that of Production Example 1 was performed. Then, with the gas outlet closed, the Ti precursor (TDMA)Ti (tetrakisdimethylamido Titanium) was supplied as an inorganic precursor onto the organic precursor layer through the gas inlet without a carrier gas until the pressure inside the chamber reached 1 Torr (inorganic precursor supply step). The chamber inlet was then closed, and the chamber pressure was maintained at 1 Torr. The Ti precursor was reacted on the surface of the organic precursor layer for 1 second (inorganic precursor exposure step). Then, with both the gas inlet and gas outlet open, argon purge gas was supplied into the gas inlet for 300 seconds to purge reaction by-products and residual reaction gas (inorganic precursor purge step). The inorganic precursor supply step, inorganic precursor exposure step, and inorganic precursor purge step constitute an inorganic precursor subcycle.

[0153] A unit cycle consisting of one inorganic precursor subcycle and one organic precursor subcycle was repeated 42 times to form a multilayer molecular film photoresist having a thickness of approximately 20 nm.

[0154] 9 is a graph showing the film formation rate as a function of the supply time of each precursor when producing the photoresist according to Production Example 1. The graph on the left shows the change in film formation rate observed while the supply time of DEZ was changed with the DMP supply time fixed at 5 seconds, while the graph on the right shows the change in film formation rate observed while the supply time of DMP was changed with the DEZ supply time fixed at 2 seconds.

[0155] 9, the deposition rate saturates after about 2 seconds of DEZ supply and about 5 seconds of DMP supply. Furthermore, when the DEZ supply time was set to 2 seconds and the DMP supply time was set to 5 seconds, a deposition rate of about 6 Å / cycle was obtained.

[0156] FIG. 10 is a graph showing the change in film thickness depending on the number of cycles of the photoresist according to Production Example 1, and an AFM image of the surface.

[0157] Referring to FIG. 10, the photoresist according to Preparation Example 1 exhibited a film formation rate of 6 Å / cycle and realized a surface with little surface roughness.

[0158] 11 is an SEM image taken after patterning the photoresist obtained in Production Example 1. Specifically, a voltage of 100 kV, a beam current of 500 pA, and a beam current of 1500 μC / cm were applied to the photoresist obtained in Production Example 1. 2 Under the dose condition of e - After exposure to the beam, the film was immersed in 2 wt% TMAH (Tetramethylammonium horoxide) in H2O for 2 minutes, and then developed by immersion in H2O for 10 seconds.

[0159] 11, a pattern having a line width of 1 μm half pitch is clearly formed. Since the pattern is formed in the exposed area, the photoresist according to this embodiment can be defined as a negative photoresist.

[0160] FIG. 12 is a schematic diagram showing cross-linking in the photoresist during the exposure process of FIG.

[0161] 12, it can be inferred that in the irradiated region, the unreactive functional group of the inorganic monolayer bonded to the side of the organic monolayer, i.e., the ethyl group, reacted with the unreactive functional group of the adjacent organic monolayer, i.e., the thiol group, to form a Zn-SC bond. In addition, it is inferred that the Zn in the organic-inorganic monolayer coordinated with O and / or S in the adjacent organic monolayer.

[0162] It is presumed that the exposed areas due to the Zn-SC bond and coordinate bond remain undeveloped and form a pattern.

[0163] 13 is a graph showing the sensitivity to electron beams of the photoresist obtained in Production Example 1. Specifically, the photoresist obtained in Production Example was subjected to irradiation with 5 to 200 mJ / cm 2 2 After exposure under the EUV dose condition, the film was immersed in 2 wt% TMAH (Tetramethylammonium hydroxide) in H2O for 2 minutes, and then immersed in H2O for 10 seconds for development.

[0164] Referring to FIG. 13, in this experiment, the normalized thickness of the negative photoresist was shown as 1 when the thickness immediately after deposition was maintained even after development, but the multilayer molecular film photoresist according to the manufacturing example was about 150 mJ / cm 2 It can be seen that the thickness normalized by ρ is excellent.

[0165] Fig. 14 is a schematic diagram showing the form and dose conditions for EUV irradiation, and Fig. 15 is an optical photograph of the photoresist pattern obtained after irradiating the photoresist of Production Example 1 with the EUV pattern shown in Fig. 14. Specifically, after irradiating and exposing the photoresist of Production Example 1 with the EUV pattern shown in Fig. 14, the photoresist was immersed in 2 wt% TMAH (Tetramethylammonium hydroxide) in H2O for 2 minutes, and then developed by immersion in H2O for 10 seconds.

[0166] 14 and 15, the photoresist according to the manufacturing example exhibited a thickness of about 20 nm immediately after deposition, and when exposed using EUV, exhibited a radiation energy of about 15 mJ / cm 2 2 When exposed and developed at a dose of 100 mJ / cm or more, the photoresist exhibits a thickness of about 10 nm or more. This indicates that the EUV sensitivity of the photoresist according to Production Example 1 is 15 mJ / cm. 2 It can be seen that...

[0167] FIG. 16 is a graph showing the change in film thickness depending on the number of cycles of the photoresist according to Production Example 2, and an AFM image of the surface.

[0168] Referring to FIG. 16, the photoresist according to Preparation Example 2 exhibited a film formation rate of 6.5 Å / cycle and realized a surface with little surface roughness.

[0169] FIG. 17 is a graph showing the change in film thickness depending on the number of cycles of the photoresist according to Production Example 3, and an AFM image of the surface.

[0170] Referring to FIG. 17, the photoresist according to Preparation Example 3 exhibited a film formation rate of 4.8 Å / cycle and realized a surface with little surface roughness.

[0171] Although the present invention has been described in detail above by way of preferred embodiments, the present invention is not limited to the above embodiments, and various modifications and alterations can be made by those skilled in the art within the technical spirit and scope of the present invention.

Claims

1. The molecular beam includes a plurality of molecular beams extending above a substrate and arranged laterally, each of the molecular beams including linearly linked monomolecules represented by the following chemical formula 1: 【Chemistry 1】 In Formula 1, one of the *'s is a bond to a functional group in the lower monolayer, and the other is a bond to a functional group in the upper monolayer; OM is an organic monolayer; MM is a main inorganic monolayer containing a metal atom; m is 1 to 2; n is 1 to 2; and l is 1 to 1000. A multilayer molecular film photoresist comprising a lateral inorganic monomolecule having a metal atom, the lateral inorganic monomolecule being located between the molecular beams and bonded to a side of the organic monomolecule (OM) in one of the molecular beams, and a crosslinkable functional group being bonded to a side of the organic monomolecule (OM) in another molecular beam.

2. 2. The multilayer molecular film photoresist of claim 1, wherein van der Waals interactions exist between the organic monomolecules in the laterally adjacent molecular beams.

3. 2. The multilayer molecular film photoresist according to claim 1, wherein the main inorganic monomer is an inorganic monomer represented by the following chemical formula 2: 【Chemistry 2】 In Formula 2, one of the *'s represents a bond to a functional group in the lower monolayer, and the other represents a bond to a functional group in the upper monolayer; X ａ is O, S, Se, NR (where R is H or CH ３ ) or PR (R is H or CH ３ ) and M ０ is Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W, or Si as the metal atom, Z １ and Z ２ are each independently a direct bond, a C1 to C20 substituted or unsubstituted linear or branched alkylene group, a C1 to C20 substituted or unsubstituted linear or branched alkylene oxide, a C1 to C20 substituted or unsubstituted linear or branched alkyleneamino, a C1 to C20 substituted or unsubstituted linear or branched alkylenesilylamino, a C1 to C20 substituted or unsubstituted linear or branched alkylenethio, a C1 to C20 substituted or unsubstituted linear or branched alkyleneseleno, or a C1 to C20 substituted or unsubstituted linear or branched alkylenephosphino; L ａ and L ｂ are each independently a halogen group, a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, a C1 to C5 alkylphosphino group, acetate, or allyloxy; The sum of na and nb is an integer of 0 to 4.

4. 4. The multilayer molecular film photoresist according to claim 3, wherein na and nb are both 0.

5. 2. The multilayer molecular film photoresist according to claim 1, wherein the side inorganic monolayer is an inorganic monolayer represented by the following chemical formula 3: 【Transformation 3】 In the above Chemical Formula 3, * represents a bond to the organic monolayer, X ｃ is O, S, Se, NR (where R is H or CH ３ ) or PR (R is H or CH ３ ) and M ０ is Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W, or Si as the metal atom, Z １ and Z ２ are each independently a direct bond, a C1 to C20 substituted or unsubstituted linear or branched alkylene group, a C1 to C20 substituted or unsubstituted linear or branched alkylene oxide, a C1 to C20 substituted or unsubstituted linear or branched alkyleneamino, a C1 to C20 substituted or unsubstituted linear or branched alkylenesilylamino, a C1 to C20 substituted or unsubstituted linear or branched alkylenethio, a C1 to C20 substituted or unsubstituted linear or branched alkyleneseleno, or a C1 to C20 substituted or unsubstituted linear or branched alkylenephosphino; L ａ and L ｂ are each independently a halogen group, a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, a C1 to C5 alkylphosphino group, acetate, or allyloxy; The sum of na and nb is an integer from 0 to 4, R ｂ２ is a halogen group (e.g., Cl, Br, or I), a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy, a C1 to C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, or a C1 to C5 alkylphosphino group.

6. 6. The multilayer molecular film photoresist according to claim 5, wherein na and nb are both 0.

7. The crosslinkable functional group is *-Z ５ X ｃ R ａ３ and where * is a bond to the organic monomolecule, and Z ５ is a direct bond or a C1-C5, specifically C1-C3, substituted or unsubstituted, linear or branched alkylene group; X ｃ is O, S, Se, NR (where R is H or CH ３ ) or PR (R is H or CH ３ ) and R ａ３ 2. The multilayer molecular film photoresist according to claim 1, wherein is hydrogen or a C1-C2 alkyl group.

8. The multilayer molecular film photoresist according to claim 1 , wherein the organic monomer is represented by the following chemical formula 4: 【Chemistry 4】 In Chemical Formula 4, one of the *'s is a bond to a functional group in the lower monolayer, and the other is a bond to a functional group in the upper monolayer. X ｂ is O, S, Se, NR (where R is H or CH ３ ) or PR (R is H or CH ３ ) and Z ３ and Z ４ are each independently a direct bond or a C1-C5 linear or branched alkylene group, MR is a backbone having a linear chain of 2 to 7 carbons or a non-aromatic or aromatic ring of 3 to 18 carbons; The side inorganic monomers or the crosslinkable functional groups are bonded to the backbone (MR).

9. 9. The multilayer molecular film photoresist according to claim 8, wherein MR is a C2 to C6 linear alkylene group.

10. a plurality of molecular beams each extending above a substrate and arranged laterally, each molecular beam including monomolecules linearly linked together, the monomolecules including a plurality of main inorganic monomolecules each including a metal atom and an organic monomolecule linked between at least some of the main inorganic monomolecules; A multi-layer molecular film photoresist including a lateral inorganic monomolecule having a metal atom, the lateral inorganic monomolecule being located between the molecular beams and bonded to a side of the organic monomolecule.

11. The main inorganic monomolecules and organic monomolecules located within the molecular beam are -O-, -S-, -Se-, -NR- (R is H or CH ３ ) and -PR- (R is H or CH ３ 11. The multilayer molecular film photoresist of claim 10, wherein the groups are linked by a bond selected from the group consisting of:

12. The organic monolayer and the inorganic monolayer on the side are each independently selected from —O—, —S—, —Se—, and —NR— (wherein R is H or CH ３ ) and -PR- (R is H or CH ３ 11. The multilayer molecular film photoresist of claim 10, wherein the groups are linked by a bond selected from the group consisting of:

13. 11. The multilayer molecular film photoresist according to claim 10, wherein the metal atom contained in the main inorganic monolayer or the side inorganic monolayer is Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Ti, Cu, W, or Si.

14. 11. The multilayer molecular film photoresist of claim 10, wherein van der Waals interactions exist between the organic monomolecules in laterally adjacent molecular beams.

15. 11. The multilayer molecular film photoresist according to claim 10, wherein each of the molecular beams is formed by alternately stacking and bonding the main inorganic monomolecules and the organic monomolecules.

16. The multilayer molecular film photoresist of claim 10, wherein the multilayer molecular film photoresist is an EUV photoresist.

17. The molecular beam includes a plurality of molecular beams extending above a substrate and arranged laterally, each of the molecular beams including linearly linked monomolecules represented by the following chemical formula 1: 【Transformation 5】 In Formula 1, one of the *'s is a bond to a functional group in the lower monolayer, and the other is a bond to a functional group in the upper monolayer; OM is an organic monolayer; MM is a main inorganic monolayer containing a metal atom; m is 1 to 2; n is 1 to 2; and l is 1 to 1000. providing a multilayer molecular film photoresist located between the molecular beams, the multilayer molecular film photoresist including a lateral inorganic monomolecule having a metal atom and bonded to a side of the organic monomolecule (OM) in one of the molecular beams, and a crosslinkable functional group bonded to a side of the organic monomolecule (OM) in another molecular beam; irradiating a partial region of the multilayer molecular film photoresist with radiation such as E-beam or EUV to crosslink the inorganic monomolecules on the sides with the crosslinkable functional groups; developing and removing the areas of the multilayer molecular film photoresist that are not exposed to the radiation.

18. loading a substrate into a chamber including a gas inlet and a gas outlet; performing an organic precursor subcycle including supplying an organic precursor represented by the following Chemical Formula 5 into the chamber with the gas outlet closed, reacting the organic precursor on the substrate, and then purging residual reaction gas from the chamber; performing an inorganic precursor subcycle, including supplying an inorganic precursor represented by the following Chemical Formula 6 into the chamber with the gas outlet closed, reacting the inorganic precursor on the organic precursor, and then purging residual reaction gas from the chamber; performing a unit cycle including the organic precursor sub-cycle and the inorganic precursor sub-cycle several times to form a multilayer molecular film photoresist; Irradiating a partial region of the multilayer molecular film photoresist with radiation such as E-beam or EUV; developing the areas of the multilayer molecular film photoresist that are not exposed to the radiation. 【Transformation 6】 In the above formula 5, R ａ１ , R ａ２ , and R ａ３ are each independently hydrogen or a C1-C2 alkyl group, and X ａ , X ｂ , and X Ｃ are independently O, S, Se, NR (wherein R is H or CH ３ ) or PR (R is H or CH ３ ) and Z ３ , Z ４ , Z ５ are each independently a direct bond or a C1-C3 substituted or unsubstituted linear or branched alkylene group; MR is a backbone having a linear chain of 2 to 7 carbons or a non-aromatic or aromatic ring of 3 to 18 carbons; x is 1 or 2; 【Transformation 7】 In Chemical Formula 6, R ｂ１ and R ｂ２ are each independently a halogen group, a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, or a C1 to C5 alkylphosphino group; M ０ は、Sn、Sb、Te、Bi、Zr、Al、Hf、Zn、In、Al、Ti、Cu、W、またはSiであり、 Z １ and Z ２ are each independently a direct bond, a C1 to C20 substituted or unsubstituted linear or branched alkylene group, a C1 to C20 substituted or unsubstituted linear or branched alkylene oxide, a C1 to C20 substituted or unsubstituted linear or branched alkyleneamino, a C1 to C20 substituted or unsubstituted linear or branched alkylenesilylamino, a C1 to C20 substituted or unsubstituted linear or branched alkylenethio, a C1 to C20 substituted or unsubstituted linear or branched alkyleneseleno, or a C1 to C20 substituted or unsubstituted linear or branched alkylenephosphino; L ａ and L ｂ are each independently a halogen group, a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, a C1 to C5 alkylphosphino group, acetate, or allyloxy; The sum of na and nb is an integer of 0 to 4.

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