Multilayer molecular film photoresist with molecular beam structure crosslinkable by coordination bonds

Abstract

A multilayer molecular film photoresist is provided, comprising a plurality of laterally arranged molecular beams each extending above a substrate, each including a linearly linked chain of monomolecules, the monomolecules including a number of inorganic monomolecules containing a metal atom and organic monomolecules interposed between at least some of the inorganic monomolecules, and adjacent ones of the molecular beams are bridged by coordinate bonds.

Description

[Technical Field]

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

[0002] There has been continuous research into photoresists, and the most active method has been to prepare a liquid photosensitive solution and then deposit it on a substrate by spin coating.These traditional photoresists mainly use chemically amplified photoresists (CARs), which contain a polymer resin, a photo-acid generator (PAG), and a quencher.

[0003] Recently, in the semiconductor industry, extreme ultraviolet (EUV) exposure technology (Photolithography) has been developed, which uses an EUV light source and is capable of forming ultra-fine patterns of 10 nm or less. We have introduced lithography.

[0004] However, EUV has a low photon density, 1 / 14 of that of 193 nm DUV (deep UV), which leads to stochastic defects. This can cause photon shot noise, specifically photon shot failure. For example, in the case of CAR, the probability of PAG reacting is low due to low photon density, which can cause shot noise. In addition, CAR is known to have the disadvantage of exhibiting relatively large line edge roughness due to the large size of polymer resin particles, which is 4 nm or more. 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 producing the same.

[0006] The technical problems of the present invention are not limited to those mentioned above, 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 one embodiment of the present invention, there is provided a multilayer molecular film photoresist. The multilayer molecular film photoresist comprises a plurality of molecular beams each extending above a substrate and arranged laterally, each of which includes a linear chain of monomolecules, each of which includes a plurality of inorganic monomolecules containing a metal atom and an organic monomolecule interposed between at least some of the inorganic monomolecules. When irradiated with radiation, adjacent ones of the molecular beams are crosslinked by coordinate bonds. In at least some of the inorganic monomolecules, the number of side functional groups bonded to the side of the metal atom satisfies the following mathematical formula 1:

[0008] [Number 1] The number of side functional groups is less than the maximum coordination number of the metal atom −2.

[0009] Within the molecular beam, the single molecules may be connected by one bond selected from the group consisting of -O-, -S-, -Se-, -NR- (R is H or CH3), and -PR- (R is H or CH3).

[0010] The coordinate bond is also a bond between O, S, Se, N, or P in -O-, -S-, -Se-, -NR- (R is H or CH3), or -PR- (R is H or CH3), which is a bond connecting a metal atom in a first molecular beam of the molecular beams and a monomolecule in a second molecular beam adjacent to the first molecular beam.

[0011] The number of side functional groups of the inorganic monomer can be 0 or 1. When the number of side functional groups of the inorganic monomer is 1 or more, the side functional group(s) can also be air-stable functional group(s). The air-stable functional group(s) can also be a C1-C5 alkyl group, acetate, aryloxy (e.g., phenyloxy), or β-diketonate ligand.

[0012] The metal atom contained in the inorganic monolayer may be Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Ti, Cu, W, or Si.

[0013] Van der Waals interactions may exist between the organic monomolecules in laterally adjacent ones of the molecular beams. In one example, the organic monomolecules have aromatic rings or linear alkylene groups, and the van der Waals interactions are π-π bonds between the aromatic rings or van der Waals interactions between the alkylene groups.

[0014] The organic monolayer may include a C2 to C6 linear alkylene group extending in the direction of extension of the molecular beam, and may further include a C1 to C2 alkyl group bonded to a side of the linear alkylene group.

[0015] Each of the molecular beams is formed by alternately stacking and bonding the inorganic monomolecules and the organic monomolecules. The inorganic monomolecules in the molecular beams are uniformly arranged in the horizontal direction to form an inorganic monomolecular layer, and the organic monomolecules in the molecular beams are uniformly arranged in the horizontal direction to form an organic monomolecular layer.

[0016] The multilayer molecular film photoresist is also an EUV photoresist.

[0017] According to one embodiment of the present invention, there is provided a multilayer molecular film photoresist, comprising a plurality of laterally arranged molecular beams each extending above a substrate, each of the molecular beams having a layer represented by the following Chemical Formula 1:

[0018] [ka] In Chemical Formula 1, one of the *'s is a bond with a functional group in the lower layer, and the other is a bond with a functional group in the upper layer, MM is an inorganic monolayer containing a metal atom, OM is an organic monolayer, m is 1 to 2, n is 1 to 2, and l is 1 to 1000.

[0019] At least some of the inorganic monomolecules included in each molecular beam have a number of side functional groups bonded to the side of the metal atom that satisfies the following equation 1: [Equation 1] Number of side functional groups<Maximum coordination number of metal atom−2.

[0020] Van der Waals interactions may exist between the organic monomolecules within the laterally adjacent molecular beams.

[0021] The organic monomer may be represented by the following Chemical Formula 2:

[0022] [ka] In the formula 2, one of the *'s is a bond to a functional group in the lower layer, and the other is a bond to a functional group in the upper layer; b is O, S, Se, NR (R is H or CH3) or PR (R is H or CH3), MR is a substituted or unsubstituted aromatic ring or a substituted or unsubstituted C1 to C18 linear, branched or cyclic alkylene group, and Z3 and Z4 are each independently a bond or a substituted or unsubstituted C1 to C5 linear or branched alkylene group.

[0023] The organic monomer represented by Chemical Formula 2 is also an organic monomer represented by Chemical Formula 2A below.

[0024] [ka] In the chemical formula 2A, Ra3 is a C1-C2 alkyl group; MR is a C1-C18 substituted or unsubstituted linear, branched, or cyclic alkylene group; n is 1 or 2; *, X b , Z3 and Z4 are as defined in Chemical Formula 2 above.

[0025] The MR may also be a C2 to C6 linear alkylene group.

[0026] The inorganic monomer may be represented by the following Chemical Formula 3:

[0027] [ka] In the formula 2, one of the *'s is a bond to a functional group in the lower layer, and the other is a bond to a functional group in the upper layer; a is O, S, Se, NR (R is H or CH3) or PR (R is H or CH3), and M 0 is the metal atom and can be Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W, or Si. Z1 and Z2 each independently represent 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 alkylene amino, a C1 to C20 substituted or unsubstituted linear or branched alkylene silyl amino, a C1 to C20 substituted or unsubstituted linear or branched alkylene thio, a C1 to C20 substituted or unsubstituted linear or branched alkylene seleno, or a C1 to C20 substituted or unsubstituted linear or branched alkylene phosphino. The sum of na and nb is an integer of 0 to 4, but may be limited to a range that satisfies the above Chemical Formula 1. a and L b are each independently a C1-C5 alkyl group, acetate, or aryloxy (e.g., phenyloxy); or when the sum of na and nb is 2 or more, L a and / or L bTwo of these are also linked to form β-diketonate ligands.

[0028] Both na and nb can also be 0.

[0029] According to one embodiment of the present invention, there is provided a multilayer molecular film photoresist pattern comprising a plurality of molecular beams extending above a substrate and arranged laterally, each of the molecular beams including linearly linked monomolecules, the monomolecules including a plurality of inorganic monomolecules including a metal atom and organic monomolecules interposed between at least some of the inorganic monomolecules, and adjacent ones of the molecular beams are bridged by coordinate bonds.

[0030] Within the molecular beam, the monomolecules are connected by one bond selected from the group consisting of -O-, -S-, -Se-, -NR- (R is H or CH3), and -PR- (R is H or CH3), and the coordinate bond is also a bond between O, S, Se, N, or P in -O-, -S-, -Se-, -NR- (R is H or CH3), or -PR- (R is H or CH3), which is a bond connecting a metal atom provided in a first molecular beam of the molecular beams to a monomolecule provided in a second molecular beam adjacent to the first molecular beam. [Effects of the Invention]

[0031] The multilayer molecular film photoresist according to one embodiment of the present invention can separate molecular beams rather than particles during exposure and development, which can significantly reduce line edge roughness (LER), which refers to the roughness of the pattern sidewalls, during EUV patterning and significantly improve resolution.

[0032] In addition, the multilayer molecular film photoresist can exhibit low stochastic failure and high photosensitivity even to EUV, which has a low photon density.

[0033] Furthermore, after the photoresist is formed, a reaction occurs inside the photoresist due to moisture during storage, which can prevent the formation of cross-links. [Brief explanation of the drawings]

[0034] [Figure 1] 1 is a schematic diagram illustrating a multilayer molecular film photoresist having a vertical molecular beam structure according to one embodiment of the present invention. [Figure 2] 1 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 3] 1A-1D are schematic diagrams illustrating sequential steps of a photolithography method according to one embodiment of the present invention. [Figure 4] 1A-1D are schematic diagrams illustrating sequential steps of a photolithography method according to one embodiment of the present invention. [Figure 5] 1A-1D are schematic diagrams illustrating sequential steps of a photolithography method according to one embodiment of the present invention. [Figure 6] 1A-1D are schematic diagrams illustrating sequential steps of a photolithography method according to one embodiment of the present invention. [Figure 7] 1A-1D are schematic diagrams illustrating sequential steps of a photolithography method according to one embodiment of the present invention. [Figure 8] 1 is a graph showing the film formation rate as a function of the supply time of each precursor when producing a photoresist according to a production example. [Figure 9] This is an SEM image taken after patterning the photoresist obtained in the manufacturing example. [Figure 10] 1 is a graph showing the sensitivity of the photoresist obtained in the manufacturing example to an electron beam. [Figure 11] 1 is a schematic diagram showing the form and dose conditions for EUV irradiation. [Figure 12] 12 is an optical photograph of a photoresist pattern obtained after irradiating the photoresist according to the manufacturing example with an EUV pattern as shown in FIG. 11. [Figure 13]This is an SEM image of a photoresist pattern obtained by irradiating the photoresist of the manufacturing example with EUV and then developing it. [Figure 14] 1 shows O1sXPS (X-ray Photoelectron spectroscopy) analysis data of a photoresist according to a manufacturing example before EUV exposure. [Figure 15] 1 shows O1sXPS (X-ray Photoelectron spectroscopy) analysis data of a photoresist according to a manufacturing example after EUV exposure. [Figure 16] 1 shows S2pXPS (X-ray Photoelectron spectroscopy) analysis data of a photoresist according to a manufacturing example before EUV exposure. [Figure 17] 1 shows S2pXPS (X-ray Photoelectron spectroscopy) analysis data after EUV exposure of the photoresist according to the manufacturing example. [Figure 18] 1 is an SEM image of a photoresist pattern obtained by irradiating a photoresist according to a manufacturing example with an electron beam and then developing the photoresist. [Figure 19] 1 is a SEM image of a photoresist pattern obtained by irradiating a photoresist according to a manufacturing example with EUV light having a wavelength of 13.5 nm and then developing the photoresist. DETAILED DESCRIPTION OF THE INVENTION

[0035] In this specification, the term "metal" is a concept that includes all metals, but also includes, for example, transition metals, post-transition metals, and metalloids.

[0036] In this specification, the radiation may be, for example, EUV or E-beam, but is not limited thereto depending on the case.

[0037] 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.

[0038] As used herein, when molecules or functional groups are "linked by a bond," it means that they are directly linked (directly bonded) or indirectly linked (indirectly bonded) through the placement of another molecule(s) or functional group between them.

[0039] In this specification, when it is stated that "the number of carbon atoms (C)X to the 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 the number of carbon atoms X and the number of carbon atoms Y. For example, when it is stated as C1 to C10, it should be understood that it describes all of C1, C2, C3, C4, C5, C6, C7, C8, C9, and C10.

[0040] In this specification, when "X to Y" is stated, it should be interpreted that all integers between X and Y are also stated. For example, when 1 to 10 is stated, it should be interpreted that 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 are all stated.

[0041] In this specification, the term "aromatic ring" refers to a 5- to 14-membered, specifically 5- or 6-membered, aromatic ring, which may have a homocyclic structure in which all the members are carbon, or a heterocyclic structure in which some of the members are substituted with heteroelements.

[0042] In this specification, the "alkylene group" or "alkyl group" means that all elements constituting the main chain are carbon, and some carbon atoms are substituted with O, S, N, C=O, or Si. The substituted elements are not limited thereto.

[0043] FIG. 1 is a schematic diagram showing a multilayer molecular film photoresist having a vertical molecular beam structure according to one embodiment of the present invention.

[0044] 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 the bare substrate or a bare substrate on which the element is formed.

[0045] 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 one of them. The metal film is used to form wiring and may be aluminum, tungsten, titanium, or a composite film containing any one of them. The semiconductor film may be a silicon film, e.g., single-crystal silicon, polysilicon, or amorphous silicon film, or a composite film containing any one of them. 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 one of them. For example, the layer to be etched 20 may be the bare substrate.

[0046] The layer to be etched 20 may have, or be surface-treated to have, a hydroxyl group, a thiol group, an amine group, or a phosphine group as examples of surface functional groups.

[0047] A multilayer molecular film photoresist 30 having a molecular beam structure may be formed on the etching layer 20 .

[0048] The multilayer molecular film photoresist 30 also includes a plurality of molecular lines ML extending laterally, each of which is formed by a direct or indirect bond between inorganic monomolecules (M1, M2, or M3). Herein, a molecular line (ML) may be defined as a backbone, molecular chain, or main chain formed by monomolecules linked by bonds. The inorganic monomolecules (M1, M2, or M3) may also be organometallic monomolecules. Herein, organometallics also include coordination compounds. In this context, "indirectly linked" may refer to the bonding of an organic monomolecule (O1, O2, or O3) or a functional group, which will be described later, between the inorganic monomolecules (M1, M2, or M3). The bond may be a covalent bond or a coordinate bond. In one example, the molecular lines ML extend upward, e.g., vertically, relative to the substrate 10, and the lateral direction may be substantially parallel to the surface of the substrate 10.

[0049] In this embodiment, the multilayer molecular film photoresist 30 is formed by atomic layer deposition or molecular layer deposition. Since the multilayer molecular film photoresist 30 is formed using a layer deposition (LDP), most of the molecular beams ML in the multilayer molecular film photoresist 30 may have substantially the same layer structure. As a result, the molecular beams ML in the multilayer molecular film photoresist 30 may have substantially the same inorganic monolayer, specifically, an inorganic monolayer and substantially the same organic monolayer, in the lateral direction. That is, the inorganic monolayers provided in the molecular beams may be arranged substantially identically in the lateral direction to form an inorganic monolayer, and the organic monolayers provided in the molecular beams may be arranged substantially identically in the lateral direction to form an organic monolayer.

[0050] The multilayer molecular film photoresist 30 can also be an organic / inorganic multilayer molecular film photoresist. Specifically, the multilayer molecular film photoresist 30 means that organic monomolecules O1, O2, and O3 are interposed between some of the inorganic monomolecules M1, M2, and M3 contained in each molecular beam ML and bonded to each other. In this case, the multilayer molecular film photoresist 30 includes a plurality of molecular beams ML in the horizontal direction, each of which is formed by bonding organic monomolecules O1, O2, and O3 to inorganic monomolecules M1, M2, and M3. The organic monomolecules O1, O2, and O3 in adjacent molecular beams ML have van der Waals interactions VI. In this case, the van der Waals interactions VI stabilize adjacent molecular beams ML in the horizontal direction, preventing pattern collapse even in cases with a high aspect ratio. The van der Waals interactions can be, for example, van der Waals interactions between alkylene groups or π-π bonds between aromatic groups.

[0051] When the multilayer molecular film photoresist 30 is irradiated with radiation, adjacent molecular beams among the molecular beams may be crosslinked by coordinate bonds. Monomolecules within the molecular beams are connected by one bond selected from the group consisting of -O-, -S-, -Se-, -NR- (R is H or CH3), and -PR- (R is H or CH3). The coordinate bond may be a bond between O, S, Se, N, or P in -O-, -S-, -Se-, -NR- (R is H or CH3), or -PR- (R is H or CH3), which connects a metal atom in a first molecular beam among the molecular beams to a monomolecule in a second molecular beam adjacent to the first molecular beam. In this case, the number of side functional groups bonded to the side of the metal atom in at least some of the inorganic monomolecules may satisfy the following Equation 1:

[0052] [Number 1] The number of side functional groups is less than the maximum coordination number of the metal atom −2.

[0053] Each molecular beam of the multilayer molecular film photoresist 30 may have a layer structure represented by the following Chemical Formula 1.

[0054] [ka] In Chemical Formula 1, one of the *s can be a bond with a functional group in a lower layer within the molecular beam or a functional group in a lower monolayer, and the other can be a bond with a functional group in an upper layer or a functional group in an upper monolayer. In this case, the bond can be, for example, a covalent bond. OM can be an organic monolayer. MM can be an inorganic monolayer containing a metal element, specifically an organometallic monolayer. In Chemical Formula 1, m is 0 to 10, n is 1 to 10, and l is 1 to 10,000, specifically 20 to 1,000, and more specifically 25 to 100. Specifically, m can be 1 to 2, for example, m can be 1. n is also 1 to 2, for example, n can be 1. Chemical Formula 1 means that an organic monolayer (OM) and an inorganic monolayer (MM) are sequentially stacked on a lower layer, and that an inorganic monolayer (MM) and an organic monolayer (OM) are sequentially stacked on a lower layer.

[0055] In FIG. 1, O1, O2, and O3 are all organic monolayers (OM) and represent different organic monolayers, but are not limited thereto, and the organic monolayers in each layer (FL1, FL2, FL3) are all the same. Also, in FIG. 1, M1, M2, and M3 are all inorganic monolayers (MM) and represent stacks of different inorganic monolayers, but are not limited thereto, and the inorganic monolayers in each layer (FL1, FL2, FL3) are all the same. Also, in FIG. 1, n1, n2, and n3 are each independently the same as the n value in Formula 1, m1, m2, and m3 are each independently the same as the m value in Formula 1, and l1, l2, and l3 are each independently the same as the l value in Formula 1.

[0056] Specifically, the organic monolayer (OM) may have an aromatic ring or a linear, branched, or cyclic alkylene group as a main body, and may be bonded to a lower layer or a lower inorganic monolayer (MM) through O, S, Se, NR (R is H or CH3), or PR (R is H or CH3) bonded directly or indirectly to one end of the main body. The OM may further include a C1-C2 alkyl group(s) bonded directly or indirectly to a side of the main body. The linear or branched alkylene group may extend in substantially the same direction as the extension direction of the molecular beam ML, and the major axis of the ring may be in substantially the same direction as the extension direction of the molecular beam ML.

[0057] For example, the OM may be an organic monolayer represented by the following formula 2: When m is 2 or more or L is 2 or more in formula 1, the organic monolayers (OM) of each layer may be the same or different from each other.

[0058] [ka] In the formula 2, one of the *'s may be a bond with a functional group in a lower layer within the molecular beam or a functional group in a lower organic or inorganic monolayer, and the other may be a bond with a functional group in an upper layer within the molecular beam or a functional group in an upper organic or inorganic monolayer. In this case, the bond may be, for example, a covalent bond. X b is also O, S, Se, NR (R is H or CH), or PR (R is H or CH). b is also O or S.

[0059] Z3 and Z4 are each independently a bond or a C1 to C5 substituted or unsubstituted linear or branched alkylene group.

[0060] MR in Formula 2 may be an aromatic ring, a C1-C18, specifically a C2-C6 linear, branched, or cyclic alkylene group, as the main body of the organic monomolecule (OM). In one embodiment, MR may be a linear alkylene group. In this case, the linear alkylene group extends in substantially the same direction as the molecular beam.

[0061] When MR is an aromatic ring or a cyclic alkylene group, Z3 and Z4 are each independently a bond or a substituted or unsubstituted C1-C5 linear or branched alkylene group, where the substitution can be achieved by replacing a hydrogen atom of the alkylene group with various functional groups, such as OH, SH, SeH, NR2 (where R is independently H or CH3), or PR2 (where R is independently H or CH3).

[0062] When MR is a C1 to C18, specifically C2 to C6, straight or branched alkylene group, Z3 and Z4 are also bonds.

[0063] As defined above, all of the elements constituting the main chain of the alkylene group are carbon, and some of the carbon atoms may be substituted with O, S, N, C═O, or Si; however, the substituted elements are not limited thereto.

[0064] In one example, the organic molecule (OM) is a R bonded directly or indirectly to the side of the body (MR). a3 R a3 is also a C1-C2 alkyl group as a substituent of MR. a3 If there are multiple, R a3 are the same or different from each other. n is 0 to 4, for example, 1 to 2. When n is O, the hydrogen of MR is R a3 It can mean that the R is not substituted, but remains as is, or is substituted with another functional group. a3 can be bonded to a carbon atom in MR or to an N or Si atom introduced by substituting a carbon atom. When n is 2 or more, R a3 R may be bonded to the same member in MR or to different members. If bonded to the same member, the number of R may be limited to the number of covalent bonds that can be made to that member. a3 When MR is a linear alkylene group, when Z4 or a direct bond is a member of MR, X in the following chemical formula 3 a It can be linked to an α-member, a β-member, or a γ-member on a γ-member basis.

[0065] MR in the formula 2 is R a3 In addition, various functional groups, specifically functional groups capable of being crosslinked by radiation, may be substituted with functional groups including vinyl groups, or OH, SH, SeH, NR2 (where R is independently H or CH3), or PR2 (where R is independently H or CH3). In one example, MR in Formula 2 is R a3 Outside, there is no substitution.

[0066] MM in Chemical Formula 1 can be an inorganic monolayer containing a metal atom, specifically, an organometallic monolayer. For example, MM can be a light-absorbing inorganic monolayer containing a metal atom with 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, Si, or Zn. The metal atom with a d orbital, specifically, a 4d or 5d orbital, can be, for example, Sn, Sb, Te, or Bi. Here, the classification of inorganic monolayers refers to their main functions, and all of the inorganic monolayers listed can perform light absorption and photoreaction.

[0067] Inorganic monomolecules are composed of a central metal (M 0 ) and at least two functional groups, and can be bonded to the lower layer or the organic monolayer (OM) through O, S, Se, NR (R is H or CH3), or PR (R is H or CH3) directly or indirectly bonded to one end of the functional group. 0 ) can be directly or indirectly bonded to the underlying layer or underlying organic monolayer (OM) through O, S, Se, NR (R is H or CH3), or PR (R is H or CH3).

[0068] In one example, the inorganic monolayer may have no side functional groups protruding from the sides of the molecular beam other than the functional groups that directly or indirectly bond with the upper and lower monolayers within the molecular beam, or may have side functional groups that are highly stable against moisture in the air. Here, the term "functional group" encompasses organic functional groups, inorganic functional groups, and ligands. "Stable against moisture" means that no reaction occurs due to moisture. Such side functional groups are suitable for bonding with the central metal (M 0 If the inorganic monomer does not have a side functional group or has an air-stable side functional group(s), it can prevent cross-linking due to a reaction with moisture inside the photoresist during storage after photoresist formation.

[0069] Specifically, the MM is an inorganic monomolecule represented by the following formula 3:

[0070] [ka] In Formula 3, one of the *'s may be a bond with a functional group in a lower layer within the molecular beam or a lower organic or inorganic monolayer (specifically, its functional group), and the other may be a bond with a functional group in an upper layer or an upper organic or inorganic monolayer (specifically, its functional group). In this case, the bond may be, for example, a covalent bond.

[0071] Z1 and Z2 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.

[0072] M 0 is 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, is, for example, Sn, Sb, Te, or Bi.

[0073] X a is also O, S, Se, NR (R is H or CH), or PR (R is H or CH). a is also O or S.

[0074] L a and L b is M 0The sum of the numbers of ligands, na and nb, is M 0 The maximum coordination number is determined by the maximum coordination number resulting from the above, and is equal to or smaller than the maximum coordination number minus two (the number taking into account Z1 and Z2). 0 For example, the sum of na and nb is an integer between 0 and 4. a and L b are each independently 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 can be selected independently 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 them are attached to the M 0 Z, Z, L may be taken together 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.

[0075] In one example, the central metal of MM (M 0 ) is a side functional group (L a and L b If the functional group(s) is / are either absent (both na and nb are O) or present (na and / or nb are 1 or more), the functional group(s) is / are also air-stable, i.e., highly stable to moisture in the air. a and L bare each independently a C1-C5 alkyl group, a C1-C2 alkylsilylamino group, acetate, or aryloxy (e.g., phenyloxy); or when the sum of na and nb is 2 or more, L a and / or L b Two of these can combine to form a β-diketonate ligand, for example, an acetylacetonate ligand.

[0076] In one example, M 0 When is Zn, na and nb are both O. M 0 When is Ti or Ni, na and nb are both 2, and the side functional groups are two L a and two L b are the two β-diketonates formed by the combination of M 0 If is Hf, L a and L b are independently acetate, aryloxy (e.g., phenyloxy), or na and nb are both 2, and the side functional groups are two L a and two L b are also the two β-diketonates formed by the combination of M 0 If is Si, L a and L b Each of M is also a C1 to C5 alkyl group. 0 is Al, Sb, or Sn, L a and L b are each independently a C1-C5 alkylamino group, a C1-C5 alkyl group, a C1-C2 alkylsilylamino group, acetate, or aryloxy (e.g., phenyloxy); or when the sum of na and nb is 2 or more, L a and / or L b Two of Z1, Z2, and L can combine to form a β-diketonate ligand. a , or L b and M 0 Each bond between may be a covalent bond or a coordinate bond, independently of the other.

[0077] Specific examples of the inorganic monomolecules are as follows:

[0078] [ka] 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 distinguished depending on the type of inorganic monolayer, specifically, organometallic monolayer. For example, the multilayer molecular film photoresist 30 may include one, two, or three of these layers. The distinction of each layer indicates a distinct primary function, and all layers may generate secondary electrons through light absorption and perform a photoreaction, as described below. For example, the multilayer molecular film photoresist 30 may include at least a light-absorbing layer FL1. 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.

[0079] The van der Waals interactions VI between adjacent organic molecules (OM, O1, O2, or O3) in the molecular beams ML stabilize the laterally adjacent molecular beams ML, preventing pattern collapse even in the case of a high aspect ratio. In one example, the van der Waals interactions are van der Waals interactions between alkylene groups or π-π bonds between aromatic groups.

[0080] As described above, the organic monolayer (OM) is a C1-C2 alkyl group (R) (R in Chemical Formula 2) directly or indirectly bonded to the side of the main body (MR in Chemical Formula 2). a3 ), the molecular beams can maintain an appropriate distance due to the steric effect thereof, and the van der Waals interactions between the organic single molecules (OM) can be further increased.

[0081] FIG. 2 is a schematic diagram showing an apparatus for manufacturing a multilayer molecular film photoresist having a vertical molecular beam structure according to one embodiment of the present invention.

[0082] 1 and 2, a substrate S may be loaded onto a stage 102 in a chamber 100 having a gas inlet 120 and a gas outlet 140. The substrate S may also be the substrate 10 on which the to-be-etched layer 20 described with reference to FIG.

[0083] 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., 70 to 150° C., 90 to 140° C., or 100 to 130° C. The gas outlet 140 may be connected to a vacuum pump.

[0084] 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 create a vacuum inside the chamber 100.

[0085] Thereafter, the multilayer molecular photoresist 30 can be formed by performing a cycle including a step of forming an inorganic monolayer (MM) and a step of forming an organic molecular layer (OM). Although a unit cycle of forming an inorganic monolayer (MM) after forming an organic molecular layer (OM) is described herein, this concept includes forming an inorganic monolayer (MM) after forming an organic molecular layer (OM) when performing this unit cycle.

[0086] In the step of forming the organic molecular layer (OM), an organic molecular layer unit cycle may be performed, which includes an organic precursor dodging step of dodging an organic precursor to chemically bond the organic precursor to a lower layer in a self-assembly manner; and a purging step of supplying a purge gas to purge unreacted organic precursors and reaction products.

[0087] The organic precursor has an aromatic ring or a linear or branched alkylene group (main body), and an OR bonded directly or indirectly to one end of the aromatic ring. a1 , S.R. a1 , SeR a1 , NRR a1 (R is H or CH3) or PRR a1 (R is H or CH3), and an OR bonded directly or indirectly to the other end a2 , S.R. a2 , SeR a2 , NRR a2 (R is H or CH3) or PRR a2 (R may comprise H or CH3), where R a1 and R a2 are each independently hydrogen or a C1-C2 alkyl group. The organic precursor may further include C1-C2 alkyl group(s) directly or indirectly bonded to the side of the body.

[0088] In one example, the organic precursor may be represented by the following Chemical Formula 4:

[0089] [ka] In the above formula 4, R a1 and R a2 are each independently hydrogen or a C1-C2 alkyl group, and X b and X a are each independently O, S, Se, NR (where R is H or CH3) or PR (where R is H or CH3). b is X a It is also an element with a higher reactivity than X. b is O and X a is S. On the other hand, Z3, Z4, R a3 , n, and MR are as defined in Chemical Formula 2 above. a3 When MR is a linear alkylene group, among the members of MR, when Z4 or Z4 is a direct bond, X a It can be linked to an α-member, a β-member, or a γ-member on a basis of .

[0090] Specific examples of the organic precursor are as follows:

[0091] [ka] In the organic precursor dodging step, a reaction according to the following Reaction Scheme 1 may occur.

[0092] [ka] [Reaction Scheme 1] In the above reaction formula 1, R represents a functional group on the surface of the lower layer, or a surface functional group of the lower monolayer, specifically, a surface functional group of the lower inorganic monolayer (R b2 ) where R0 is 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 alkylphosphino group. R a1 X b -Z3-MR(-Z4-X a R a2 )(-R a3 ) n is an organic precursor, and each functional group is as defined in Chemical Formula 4. b and X a When X are different from each other, the more reactive functional group can bond with the surface functional group of the lower layer. b and X a When are O and S, respectively, O can bond with the underlying surface functional group.

[0093] Referring to Reaction Scheme 1, the organic precursor can react with the functional groups on the surface of the underlayer to self-assemble onto the underlayer. a1 may be generated as a reaction by-product. Subsequently, in a purge step, the remaining excess organic precursor and the reaction by-product may be purged.

[0094] In the organic precursor dodging step, the organic precursor control valve 134 is opened, and the gas outlet valve 142 is closed, and the organic precursor can be supplied from the organic precursor storage unit 114 into the chamber 100 (organic precursor supply step). The organic precursor can be stored in the organic precursor storage unit 114 in a solid, liquid, or gaseous state. The organic precursor storage unit 114 can be heated, and the organic precursor can be supplied into the chamber 100 at a predetermined vapor pressure. In one embodiment, the organic precursor can be supplied without a carrier gas. That is, the organic precursor can be supplied alone into the chamber 100.

[0095] Since the organic precursor is supplied with the gas outlet valve 142 closed, it accumulates in the chamber 100 and increases 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 may be a pressure of the organic 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, 130 mTorr to 3 Torr, 150 mTorr to 1 Torr, 500 mTorr to 2.7 Torr, or 1.5 Torr to 2.5 Torr. Generally, the precursor is dodged into the chamber together with a carrier gas. In this case, considering that the partial pressure of the precursor is about 1 to 10 mTorr, a pressure of the organic precursor alone within the chamber 100 of 50 mTorr or more indicates a pressurized state of the organic precursor.

[0096] When the reaction pressure is reached, the organic precursor control valve 134 is closed, and the gas outlet valve 142 is closed to seal the chamber for a predetermined period of time (organic precursor exposing step). The organic precursor supplying step and the organic precursor exposing step are referred to as an organic precursor dodging step. However, the organic precursor exposing step may be omitted depending on the circumstances. During the organic precursor dodging step, the reaction according to Reaction Scheme 1 may occur.

[0097] Thereafter, the chamber 100 may be purged (organic precursor purging step). Specifically, the purge gas control valve 132 and the gas outlet valve 142 may be opened to allow the purge gas in the purge gas storage unit 112 to flow onto the substrate surface to remove excess unreacted organic precursor and the reaction by-products. In this case, the purge gas may be an inert gas, such as argon (Ar), nitrogen (N), or a combination thereof.

[0098] In the step of forming the inorganic monolayer (MM), a unit cycle may be performed, which includes a metal precursor dodging step of dodging a metal precursor to chemically bond the metal precursor to the lower layer in a self-assembly manner; and a purge step of supplying a purge gas to purge unreacted metal precursor and reaction products.

[0099] The metal precursor may also be an organometallic monolayer having at least two functional groups or ligands, and may be represented by the following Chemical Formula 5:

[0100] [ka] In the above formula 5, R b1 and R b2 are each independently 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 straight-chain or branched alkyl group. Z1, Z2, and L a , L b , n a , n b , and M 0 is as defined in Formula 3. In addition, optionally, R b1 , R b2 , L a , and L b Two of them are directly or indirectly linked M0 Z, Z, L may be taken together to form a heterocyclyl or heteroaryl. a , or L b and M 0 Each bond between R and R may be, independently of the other, a covalent or coordinate bond. b1 and R b2 At least one of the 0 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 identical functional groups, and R b1 and R b2 are the same functional groups, but L a and R b1 are also different functional groups.

[0101] The inorganic precursors are prepared by adding side functional groups (L a and L b If the functional group(s) is / are absent (both na and nb are O) or if the functional group(s) is / are present (na and / or nb are 1 or more), the functional group(s) is / are also air-stable, i.e., highly stable to moisture in the air. a and L b are each independently a C1-C5 alkyl group, acetate, or aryloxy (e.g., phenyloxy); or when the sum of na and nb is 2 or more, L a and / or L b Two of these can combine to form a β-diketonate ligand, for example, an acetylacetonate ligand.

[0102] In one example, M 0 When is Zn, both na and nb are also O. 0 When is Ti, na and nb are both 2, and the side functional groups are two L a and two Lb are also the two β-diketonates formed by the combination of M 0 If is Hf, L a and L b are independently acetate, aryloxy (e.g., phenyloxy), or na and nb are both 2, and the side functional groups are two L a and two L b are also the two β-diketonates formed by the combination of M 0 If is Si, L a and L b Each of M is also a C1 to C5 alkyl group. 0 is Al, Sb, or Sn, L a and L b are each independently a C1-C5 alkylamino group, a C1-C5 alkyl group, acetate, or aryloxy (e.g., phenyloxy); or when the sum of na and nb is 2 or more, L a and / or L b Two of these can combine to form a β-diketonate ligand.

[0103] Specific examples of the metal precursor are as follows:

[0104] [ka] In the metal precursor dodging step, a reaction according to the following Reaction Scheme 2 may occur.

[0105] [ka] [Reaction Scheme 2] In the reaction formula 2, *-X a R a2is the surface functional group of the underlayer, specifically, the surface functional group of the previously formed organic molecular layer (OM), and the metal precursor of Formula 5 can react with the surface functional group of the previously formed organic molecular layer (OM) to self-assemble on the surface of the organic molecular layer (OM). In this process, R a2 R b1 may be generated as a reaction by-product. Subsequently, the remaining metal precursor and the reaction by-product may be purged in a purging step. In Reaction Scheme 2, each functional group is the same as defined in Formulas 4 and 5.

[0106] In the metal precursor dodging step, the metal precursor gas control valve 130 is opened and the gas outlet valve 142 is closed, and the metal precursor gas can be supplied from the metal precursor storage unit 110 into the chamber 100 (metal precursor supply step). The metal precursor can be stored in the metal precursor storage unit 110 in a solid, liquid, or gaseous state. The metal precursor storage unit 110 is heated to a temperature below the thermal decomposition temperature of the metal precursor, and thus the metal precursor can be supplied into the chamber 100 at a predetermined vapor pressure. In this case, the supplied metal precursor can be supplied without a carrier gas. That is, the metal precursor can be supplied alone into the chamber 100.

[0107] Since the metal precursor is supplied with the gas outlet valve 142 closed, it may accumulate in the chamber 100 and increase the pressure within the chamber 100. The indium precursor may be supplied until the pressure within the chamber 100 reaches a reaction pressure (metal precursor supply step). In this case, the reaction pressure may be a pressure of the metal 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. Generally, the precursor is dodged into the chamber together with a carrier gas. In this case, considering that the partial pressure of the precursor is about 1 mTorr, a pressure of the metal precursor alone within the chamber 100 of 50 mTorr or more may indicate that the metal precursor is pressurized.

[0108] When the reaction pressure is reached, the metal precursor gas control valve 130 is closed to seal the chamber for a predetermined time (metal precursor exposing step). The metal precursor supplying step and the metal precursor exposing step are also called a metal precursor dodging step. However, the metal precursor exposing step may be omitted depending on the circumstances. During the metal precursor dodging step, the reaction according to Reaction Scheme 2 may occur.

[0109] Thereafter, the chamber 100 may be purged (metal precursor purging step). Specifically, the purge gas control valve 132 and the gas outlet valve 142 may be opened to allow the purge gas in the purge gas reservoir 112 to flow onto the substrate surface in the chamber to remove excess metal precursor gas and reaction by-products that are not adsorbed on the substrate surface. In this case, the purge gas may be an inert gas, such as argon (Ar), nitrogen (N), or a combination thereof.

[0110] Unlike the illustrated example, if the inorganic monolayer (MM) is composed of multiple layers (i.e., n in Formula 1 is 2 or greater), after performing the metal precursor dodging step and purging step according to Reaction Scheme 2 described above, a unit cycle including a reactant gas dodging step in which a reactant gas is dodged to react with the metal precursor chemically bonded to the lower layer, a purge step in which a purge gas is supplied to purge unreacted reactant gas and reaction products, the metal precursor dodging step, and the purge step can be repeated n-1 times. In this case, the reactant gas can be hydrogen, an oxygen-containing gas (e.g., O2, O3, HO), a nitrogen-containing gas (e.g., NH3), etc.

[0111] The control unit can control the opening and closing of the valve and the temperature of the chamber.

[0112] As such, the reaction shown in Reaction Scheme 1 may be carried out 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 be densely distributed on the substrate. The reaction shown in Reaction Scheme 1 may also be carried out with the gas outlet valve 142 closed, i.e., in a pressurized stagnant environment that is not a laminar flow environment. In this case, the organic precursor may react densely on the substrate more efficiently. However, the organic precursor may also react densely on the substrate when the gas outlet valve 142 is open to form a laminar flow in the chamber, since the organic precursor is supplied alone without a carrier gas.

[0113] In this way, when the organic precursor reacts densely on the substrate, the spacing between the organic monomolecules formed by the organic precursor becomes narrow enough to cause van der Waals interactions between them, and as a result, the main chain of the organic monomolecule (OM) is arranged upward, for example, vertically, relative to the substrate 10, and as a result, the molecular beam (ML in FIG. 1) can be arranged upward, for example, vertically, relative to the substrate 10. Meanwhile, the organic precursor is formed by forming a C1-C2 alkyl group (R in Chemical Formula 4) directly or indirectly bonded to the side of the main body (MR in Chemical Formula 4). a3 ), the molecular beams can be kept at an appropriate distance due to the steric effect of the steric effect.

[0114] The molecular layer deposition equipment according to an embodiment of the present invention may perform a cycle including a step of forming a metal monolayer (MM of Chemical Formula 1) and a step of forming an organic molecular layer (OM of Chemical Formula 1) multiple times, specifically the number of times indicated by 1 in Chemical Formula 1.

[0115] 3-7 are schematic diagrams illustrating sequential steps of a photolithography method according to one embodiment of the present invention.

[0116] 3 to 7, for the sake of convenience, Z3, Z4, and R in Chemical Formula 2 representing an organic single molecule (OM) are a3is omitted, and the case where Z1 and Z2 are omitted in chemical formula 3 representing an inorganic monomolecular (MM) is shown as an example. As a result, -[X b -MR-X a -M 0 ]- is a unit layer, the first unit layer is illustrated as a case where the sum of na and nb in Chemical Formula 3 is 0, the second unit layer is illustrated as a case where na in Chemical Formula 3 is 1 and nb is 0, and the third unit layer is illustrated as a case where na and nb in Chemical Formula 3 are both 1. However, the present invention is not limited thereto, and the stacking order may be different, or only one or two of these layers may be stacked. In addition, X in Chemical Formulas 2 and 3 b , Z3, MR, R a3 , Z4, X a , Z1, M 0 , L a , L b , and Z2 may vary depending on the unit layer. In one example, the multilayer molecular film photoresist 30 may include at least one of a light absorbing layer, a photoreactive layer, and an etching-resistant layer, which are classified according to the type of inorganic monolayer.

[0117] 3, a substrate 10 having a layer to be etched 20 formed thereon may be provided. The substrate 10 and the layer to be etched 20 may be the same as those described with reference to FIG. 1. A multilayer molecular film photoresist 30 may be formed on the layer to be etched 20. The multilayer molecular film photoresist 30 may be formed using atomic layer deposition equipment or molecular layer deposition equipment in the same manner as described with reference to FIG. 2.

[0118] As described above, the organic monolayer (OM) is a C1-C2 alkyl group (R) (R in Chemical Formula 2) directly or indirectly bonded to the side of the main body (MR in Chemical Formula 2). a3 ), the van der Waals interaction between the organic monomolecules (OM) becomes even stronger. In this case, the stronger van der Waals interaction further stabilizes the horizontally adjacent molecular beams, and pattern collapse can be prevented even in the case of a high aspect ratio. On the other hand, when the organic monomolecules (OM) further comprise C1-C2 alkyl groups (R in Chemical Formula 4) directly or indirectly bonded to the side of the main body (MR in Chemical Formula 2), a3), the molecular beams can be kept at an appropriate distance due to the steric effect of the additionally provided nuclei.

[0119] Furthermore, if the inorganic monomer does not have any side ligands or has air-stable side ligand(s), it can prevent cross-linking caused by reactions with moisture inside the photoresist during storage after photoresist formation.

[0120] Referring to FIG. 4, a portion of the multilayer molecular film photoresist 30 may be irradiated with radiation (hv), specifically, EUV or E beam. In this case, metal atoms M 0 may absorb the radiation and generate secondary electrons. However, other elements may also absorb radiation and generate secondary electrons. The generated secondary electrons may form a cross-link between adjacent molecular beams ML. Specifically, when the sum of na and nb is 0, M 0 is the X of other adjacent molecular beams. a and / or X b Specifically, it can bond to a coordinate bond (CB). When the sum of na and nb is 1, M 0 is the X of other adjacent molecular beams. a and / or X b Bonding with, specifically, coordinate bond (CB) or M 0 -L a and L a -M 0 The bond is M 0 -Y1-M 0 When the sum of na and nb is 2 or more, M 0 -L b and L a -M 0 The bond is M 0 -YM 0 wherein Y is C, O, S, Se, N, or P.

[0121] Referring to FIG. 5, the multilayer molecular photoresist 30 exposed to radiation may be exposed to a developer. In this case, the M formed in the exposed areas 0 -YM0 Combine, M 0 -Y1-M 0 Bonds (not shown), and M 0 and X a and / or X b The bonds between the adjacent molecular beams ML are not etched by the developer. Therefore, the portions other than the portions where cross-linked bonds are formed between the adjacent molecular beams ML are removed by the developer, and a multilayer molecular film photoresist pattern 31 can be formed. The developer is a developing solution, for example, water, isopropyl alcohol (IPA), or methyl isobutyl alcohol (MIL). ketone (MIBK), tetramethylammonium hydroxide (TMAH), or a developing gas, such as CF4, Ar, O2, or CHF3, or a plasma generated from them.

[0122] 6, the etching target film 20 may be etched using the multilayer molecular layer photoresist pattern 31 as a mask. This etching may be, for example, plasma etching. In this case, the etching target film 20 exposed in the area where the multilayer molecular layer photoresist pattern 31 is not present may be selectively etched by the multilayer molecular layer photoresist pattern 31, which has etching resistance due to cross-linking between adjacent molecular beams ML.

[0123] 7, the multilayer molecular film photoresist pattern 31 may be removed by using an ashing method.

[0124] As described above, in the multilayer molecular film photoresist 30 according to one embodiment of the present invention, the inorganic and organic molecules connected by bonds within the molecular beams are formed by self-assembly, so that the molecular beams grow above the substrate without being entangled with each other or growing obliquely, and the molecular beams can be uniformly arranged in the lateral direction.

[0125] The molecular beams may be formed so densely that van der Waals interactions VI exist between adjacent organic monomolecules within the molecular beams. In this case, van der Waals interactions stabilize adjacent molecular beams in the horizontal direction, preventing pattern collapse even in cases with a high aspect ratio. The formation of such dense molecular beams may be due to the organic precursor and / or metal precursor dodging being performed without using a carrier gas, thereby increasing the pressure of the organic precursor and / or metal precursor within the chamber. To this end, the organic precursor and / or metal precursor dodging may be performed with the gas outlet of the chamber closed. In this case, -[X b -MR-X a -M 0 ]-or-[X b -Z3-MR-Z4-X a -Z1-M 0 The height of the -Z2-]- unit layer (H in FIG. 3) is almost the same as the length of the unit layer, which reflects the actual size of the atoms in the unit layer and the actual length of the bonds between the atoms.

[0126] As such, the spacing between molecular beams (D in FIG. 1 or FIG. 3) is very small, less than 1 nm, specifically less than 0.5 nm. Furthermore, by separating the molecular beams, which are not particles, during exposure and development, line edge roughness (LER), which refers to the roughness of the pattern side surfaces, is very low, and resolution can be significantly improved. Furthermore, the multilayer molecular film photoresist 30 can exhibit low stochastic failure and high photosensitivity even for EUV, which has a low photon density.

[0127] In addition, the organic monolayer (OM) is a C1-C2 alkyl group (R in Chemical Formula 2) directly or indirectly bonded to the side of the main body (MR in Chemical Formula 3). a3), the van der Waals interaction between the organic monomolecules (OM) becomes even stronger. In this case, the stronger van der Waals interaction further stabilizes the horizontally adjacent molecular beams, and prevents the pattern from collapsing even when the molecular beam has a high aspect ratio. On the other hand, when the organic monomolecules (OM) further comprise C1-C2 alkyl groups (R in Chemical Formula 4) directly or indirectly bonded to the side of the main body (MR in Chemical Formula 2), a3 ), the molecular beams can be kept at an appropriate distance due to the steric effect of the additionally provided nuclei.

[0128] Furthermore, if the organometallic monolayer does not have any side ligands or has air-stable side ligand(s), it can prevent cross-linking due to reactions with moisture occurring inside the photoresist during storage after photoresist formation.

[0129] 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. Manufacturing example: Photoresist manufacturing example The substrate was loaded into a chamber equipped with a gas inlet and a gas outlet, and the substrate temperature was heated to 100°C.

[0130] With the gas outlet closed, an organic precursor, 3-Mercapto-3-methylbutan-1-ol (MMB), was supplied onto the substrate through the gas inlet without a carrier gas until the pressure inside the chamber reached 2 Torr (organic precursor supply step). The chamber inlet was then closed, and the chamber pressure was maintained at 2 Torr, allowing the organic precursor to react on the substrate for 5 seconds (organic precursor exposure step). Then, with both the gas inlet and gas outlet open, argon purge gas was supplied into the gas inlet for 800 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.

[0131] Next, with the gas outlet closed, DEZ (diethyl zinc) was supplied as a metal precursor onto the organic precursor layer through the gas inlet without a carrier gas until the chamber pressure reached 1 Torr (metal precursor supply step). Then, with the chamber inlet also closed and the chamber pressure maintained at 1 Torr, the metal precursor was reacted on the surface of the organic precursor layer for 5 seconds (metal precursor exposure step). Then, with both the gas inlet and gas outlet open, argon purge gas was supplied into the gas inlet for 200 seconds to purge reaction by-products and residual reaction gas (metal precursor purge step). The metal precursor supply step, the metal precursor exposure step, and the metal precursor purge step constitute a metal precursor subcycle.

[0132] A unit cycle consisting of one subcycle of the metal precursor and one subcycle of the organic precursor was repeated 54 times to form a multilayer molecular film photoresist having a thickness of about 20 nm.

[0133] In this case, the film formation rate was 3.7 Å / cycle. This is similar to the length of the unit reactant obtained by reacting one molecule of the Zn precursor with one molecule of the organic precursor. Therefore, when a unit cycle is performed in the photoresist production according to the Preparation Example, it can be assumed that the main chain (or molecular beam) of the reactant obtained by reacting the metal precursor and the organic precursor on the substrate will lie flat on the substrate or grow above the substrate without tilting, specifically, in a substantially vertical direction above the substrate. This means that the distance between the organic monomolecules in the molecular beam is narrow enough to allow van der Waals interactions to affect it, and even if the photoresist thickness increases due to the van der Waals interactions, the molecular beam will not tilt and will maintain substantially vertical growth.

[0134] 8 shows graphs illustrating the film formation rate as a function of the supply time of each precursor when producing a photoresist according to a manufacturing example. The graph on the left shows the change in film formation rate as the supply time of DEZ is changed while the supply time of MMB is fixed at 5 seconds, and the graph on the right shows the change in film formation rate as the supply time of MMB is changed while the supply time of DEZ is fixed at 5 seconds.

[0135] 8, the deposition rate saturates after about 4 seconds of DEZ supply time and about 5 seconds of MMB supply time. Therefore, by setting the DEZ supply time to 5 seconds and the MMB supply time to 5 seconds, a deposition rate of about 3.7 Å / cycle was obtained.

[0136] Figure 9 shows an SEM image taken after patterning the photoresist obtained in the manufacturing example. Specifically, a voltage of 15 kV, a beam current of 0.13 nA, and a dc of 300 uC / cm were applied to the photoresist obtained in the manufacturing example. 2 Under the dose conditions - After exposure to the beam, 10 wt% TMAH The film was immersed in tetramethylammonium hydroxide in H2O for 10 seconds, and then developed by immersion in H2O for 10 seconds.

[0137] 9, a half-pitch pattern having a line width of 1 μm was clearly formed. In this case, the pattern was formed in the exposed portion, and the photoresist according to this embodiment can be defined as a negative photoresist.

[0138] 10 is a graph showing the sensitivity of the photoresist obtained in the manufacturing example to an electron beam. Specifically, the photoresist obtained in the manufacturing example was subjected to irradiation with an electron beam of 5 to 200 mJ / cm. 2 After exposure under the EUV dose condition, the substrate was immersed in 10 wt% TMAH (Tetramethylammonium hydroxide) in H2O for 10 seconds, and then developed by immersion in H2O for 10 seconds.

[0139] Referring to FIG. 10, in this experiment, the normalized thickness of the negative photoresist was shown as 1 if the thickness immediately after deposition was maintained even after development, but the multilayer molecular film photoresist according to the manufacturing example had a normalized thickness of about 15 mJ / cm. 2 It can be seen that it has excellent sensitivity, showing a normalized thickness of 0.5.

[0140] Fig. 11 is a schematic diagram showing the form and dose conditions of EUV irradiation, and Fig. 12 is an optical photograph of a photoresist pattern obtained after irradiating the photoresist of the manufacturing example with the EUV pattern shown in Fig. 11. Specifically, after irradiating and exposing the photoresist of the manufacturing example with the EUV pattern shown in Fig. 11, the photoresist was immersed in 10 wt% TMAH (Tetramethylammonium hydroxide) in H2O for 10 seconds, and then developed by immersion in H2O for 10 seconds.

[0141] Referring to FIG. 12, the photoresist according to the manufacturing example has a thickness of about 20 nm immediately after deposition, and when exposed using EUV, it has a density of about 10 mJ / cm 2 2 When exposed and developed at a dose of 10 mJ / cm or more, the photoresist exhibits a thickness of about 10 nm or more. Thus, the EUV sensitivity of the photoresist according to the manufacturing example is 10 mJ / cm or more. 2 It can be seen that...

[0142] 13 is an SEM image of a photoresist pattern obtained by irradiating the photoresist of the manufacturing example with EUV and then developing it. Specifically, the photoresist of the manufacturing example was irradiated with 30 mJ / cm 2 2 After exposure to EUV, the film was immersed in 10 wt% TMAH (Tetramethylammonium hydroxide) in H2O for 10 seconds, and then developed by immersion in H2O for 10 seconds.

[0143] Referring to FIG. 13, it can be seen that a pattern having a half pitch of 20 nm line width was clearly formed.

[0144] 14 and 15 show O1s XPS (X-ray Photoelectron spectroscopy) analysis data of the photoresist according to the manufacturing example before and after EUV exposure, respectively.

[0145] Referring to FIG. 14, the O1s peak corresponding to the CO-Zn bond before exposure was shown at 531.4 eV.

[0146] Referring to Figure 15, the O1s peak corresponding to the CO-Zn bond (or O-Zn bond) after exposure is shown at 531.7 eV, which indicates that it has shifted to a higher binding energy than before exposure. This means that a coordinate bond (inset dotted line) (corresponding to C-B in Figure 4) between O and Zn has been formed in addition to the CO-Zn bond before exposure.

[0147] 16 and 17 show S2p XPS (X-ray Photoelectron spectroscopy) analysis data before and after EUV exposure of the photoresist according to the manufacturing example, respectively.

[0148] Referring to FIG. 16, the Zn-SR S2p3 peak corresponding to the Zn-SR bond before exposure was shown at 162.2 eV.

[0149] 17, the Zn-S S2p3 peak corresponding to the Zn-S bond after exposure is shown at 161.5 eV, which is shifted to a lower binding energy than the Zn-SR S2p3 peak corresponding to the Zn-SR bond before exposure, which means that a coordinate bond between S and Zn was also formed by exposure.

[0150] Table 1 below shows the XPS spectra of the photoresists produced by the manufacturing examples. The element percentages are shown through X-ray Photoelectron spectroscopy.

[0151] [Table 1] Referring to Table 1, the atomic percentages of Zn, O, and S are within a 12.5% ​​error range, with the Zn:0 atomic ratio and the Zn:S atomic ratio being approximately 1:1. This indicates that the photoresist according to the preparation example was produced by reacting the organic precursor MMB (3-Mercapto-3-methylbutan-1-ol) with the metal precursor DEZ (Diethyl zinc) in a ratio of approximately 1:1. This means that most molecular beams in the photoresist contain the same number of organic monomolecules and the same number of inorganic monomolecules, meaning that there are almost no molecular beams that end without extending due to the reaction being interrupted in the middle.

[0152] From these results, it can be inferred that when a unit cycle is carried out in the production of photoresist according to the Preparation Example, the main chain (or molecular beam) of the reactant obtained by reacting the metal precursor and the organic precursor on the substrate lies horizontally on the substrate or grows above the substrate without tilting, specifically, in a substantially vertical direction above the substrate. This means that the distance between the organic monomolecules in the molecular beam is small enough to allow van der Waals interactions to affect it, and even if the photoresist thickness increases due to the van der Waals interactions, the molecular beam does not tilt and growth in a substantially vertical direction can be maintained.

[0153] Figure 18 is an SEM image of a photoresist pattern obtained by irradiating the photoresist of the manufacturing example with an electron beam and then developing it. Specifically, a voltage of 100 kV, a beam current of 60 pA, and a fluence of 2,052 uC / cm were applied to the photoresist obtained in the manufacturing example. 2 (a, c), 2,175 uC / cm 2 (b), or 2,306 uC / cm 2 (d, e) dose condition - After exposure to the beam, 10 wt% TMAH After immersion in tetramethylammonium hydroxide in H2O for 10 seconds, the film was immersed in H2O for 10 seconds and developed to obtain a photoresist pattern.

[0154] Referring to FIG. 18, it can be seen that the photoresist according to the manufacturing example has a line edge roughness (LER) of 1.97 to 4.01 nm when exposed to an electron beam, and a pattern having a resolution (half pitch) of 12 to 30 nm can be obtained.

[0155] 19 is an SEM image of a photoresist pattern obtained by irradiating the photoresist of the manufacturing example with EUV light having a wavelength of 13.5 nm and then developing the photoresist. Specifically, the photoresist obtained in the manufacturing example was irradiated with EUV light having a wavelength of 61.75 mJ / cm. 2 (a), 65.96 mJ / cm 2 (b), 74.1 mJ / cm 2 (c), 62.29 mJ / cm 2 (d), 66.1 mJ / cm 2 After exposure under the EUV dose conditions of (e), 10 wt% TMAH After immersion in tetramethylammonium hydroxide in H2O for 10 seconds, the film was immersed in H2O for 10 seconds and developed to obtain a photoresist pattern.

[0156] Referring to FIG. 19, it can be seen that the photoresist according to the manufacturing example has a line edge roughness (LER) of 1.38 to 1.9 nm when exposed to EUV, and a pattern having a resolution (half pitch) of 12 to 16 nm can be obtained.

[0157] Although the present invention has been described in detail above with reference to preferred experimental examples, the present invention is not limited to these examples 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. a plurality of molecular beams each extending above a substrate and arranged laterally, each molecular beam including monomolecules linked in a linear chain, the monomolecules including a number of inorganic monomolecules including a metal atom and organic monomolecules interposed between at least some of the inorganic monomolecules; When irradiated with radiation, adjacent molecular beams among the molecular beams are cross-linked by coordinate bonds, At least some of the inorganic monomolecules have a number of side functional groups bonded to the side of the metal atom that satisfies the following formula 1: [Equation 1] The number of side functional groups is less than the maximum coordination number of the metal atom −2.

2. The single molecules in the molecular beam are -O-, -S-, -Se-, -NR- (wherein R is H or CH ３ ) and -PR- (R is H or CH ３ 2. The multilayer molecular film photoresist of claim 1, wherein the bond is selected from the group consisting of:

3. The coordinate bond is a bond connecting a metal atom provided in a first molecular beam of the molecular beams with a monomolecule provided in a second molecular beam adjacent to the first molecular beam, and is -O-, -S-, -Se-, -NR- (R is H or CH ３ ), or -PR- (where R is H or CH ３ 3. The multilayer molecular film photoresist according to claim 2, wherein the bond is between O, S, Se, N, or P.

4. 2. The multilayer molecular film photoresist according to claim 1, wherein the number of side functional groups of said inorganic monolayer is zero.

5. 2. The multilayer molecular film photoresist according to claim 1, wherein when the number of side functional groups of the inorganic monolayer is one or more, the side functional group(s) is / are air-stable functional group(s).

6. 6. The multilayer molecular film photoresist of claim 5, wherein the air-stable functional group(s) is a C1-C5 alkyl group, acetate, aryloxy (e.g., phenyloxy), or β-diketonate ligand.

7. 2. The multilayer molecular film photoresist according to claim 1, wherein the metal atom contained in the inorganic monolayer is Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Ti, Cu, W, or Si.

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

9. the organic monomer comprises an aromatic ring or a linear alkylene group; 9. The multilayer molecular film photoresist according to claim 8, wherein the van der Waals interactions are π-π bonds between the aromatic rings or van der Waals interactions between the alkylene groups.

10. 2. The multilayer molecular film photoresist of claim 1, wherein the organic monolayer comprises a C2 to C6 linear alkylene group extending in the extension direction of the molecular beam, and further comprises a C1 to C2 alkyl group bonded to a side of the linear alkylene group.

11. 2. The multilayer molecular film photoresist according to claim 1, wherein each of said molecular beams is formed by bonding said inorganic monomolecules and said organic monomolecules in an alternating layered manner.

12. the inorganic monomolecules provided in the molecular beam are uniformly arranged in a lateral direction to form an inorganic monomolecular layer; 2. The multilayer molecular film photoresist according to claim 1, wherein the organic monomolecules provided on the molecular beam are uniformly arranged in a lateral direction to form an organic monomolecular layer.

13. The multilayer molecular film photoresist according to claim 1 , wherein the multilayer molecular film photoresist is an EUV photoresist.

14. a plurality of laterally arranged molecular beams each extending above a substrate, each molecular beam having a layer represented by Chemical Formula 1: 【number】 In Chemical Formula 1, one of the *'s is a bond with a functional group in the lower layer, and the other is a bond with a functional group in the upper layer; MM is an inorganic monolayer containing a metal atom; OM is an organic monolayer; m is 1 to 2; n is 1 to 2; and l is 1 to 1000. At least some of the inorganic monomolecules included in each molecular beam have a number of side functional groups bonded to the side of the metal atom that satisfies the following formula 1: [Equation 1]

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

16. The multilayer molecular film photoresist of claim 14, wherein the organic monomer is represented by the following chemical formula 2: 【Chemistry 2】 In Chemical Formula 2, one of the *'s is a bond with a functional group in the lower layer, and the other is a bond with a functional group in the upper layer; X ｂ is O, S, Se, NR (where R is H or CH ３ ) or PR (R is H or CH ３ ) and MR is a substituted or unsubstituted aromatic ring or a C1 to C18 substituted or unsubstituted linear, branched, or cyclic alkylene group; Z ３ and Z ４ are each independently a bond or a C1 to C5 substituted or unsubstituted linear or branched alkylene group.

17. The multilayer molecular film photoresist according to claim 16, wherein the organic monolayer represented by Chemical Formula 2 is an organic monolayer represented by Chemical Formula 2A: 【Chemistry 2A】 In the above formula 2A, R ａ３ is a C1-C2 alkyl group, n is 1-2, *, X ｂ , M.R., Z. ３ and Z ４ is as defined in Chemical Formula 2 above.

18. 18. The multilayer molecular film photoresist according to claim 17, wherein MR is a C2 to C6 linear alkylene group.

19. The multilayer molecular film photoresist according to claim 14, wherein the inorganic monolayer is an inorganic monolayer represented by the following chemical formula 3: 【Transformation 3】 In Chemical Formula 3, one of the *'s is a bond with a functional group in the lower layer, and the other is a bond with a functional group in the upper layer; 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 the metal atom, and is Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W, or Si; 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; The sum of na and nb is an integer of 0 to 4, but is limited to a range satisfying the formula 1, L ａ and L ｂ are each independently a C1 to C5 alkyl group, acetate, or aryloxy (e.g., phenyloxy); or when the sum of na and nb is 2 or more, L ａ and / or L ｂ Two of these are linked β-diketonate ligands.

20. 20. The multilayer molecular film photoresist according to claim 19, wherein na and nb are both 0.

21. a plurality of laterally arranged molecular beams each extending above a substrate; each molecular beam includes linearly linked monomolecules, the monomolecules including a plurality of inorganic monomolecules each including a metal atom and an organic monomolecule interposed between at least some of the inorganic monomolecules; The multilayer molecular film photoresist pattern is formed by cross-linking adjacent molecular beams among the molecular beams through coordinate bonds.

22. Within the molecular beam, the monomolecules are -O-, -S-, -Se-, -NR- (wherein R is H or CH ３ ) and -PR- (R is H or CH ３ ) linked by a bond selected from the group consisting of: The coordinate bond is a bond connecting a metal atom provided in a first molecular beam of the molecular beams with a monomolecule provided in a second molecular beam adjacent to the first molecular beam, and is -O-, -S-, -Se-, -NR- (R is H or CH ３ ), or -PR- (where R is H or CH ３ 22. The multilayer molecular film photoresist pattern according to claim 21, wherein the bond is between O, S, Se, N, or P.

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