Multilayer molecular film photoresist having molecular beam structure and method for producing the same

Abstract

The multilayer molecular film photoresist includes a plurality of molecular beams each extending upwardly of a substrate and arranged laterally, each of the molecular beams being formed by bonding a plurality of inorganic monomolecules with organic monomolecules interposed between at least some of the inorganic monomolecules.

Description

[Technical Field]

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

[0002] Photoresists have been the subject of constant research, with the most active research being into the method of spin-coating a liquid photosensitive solution onto a substrate.The most commonly used traditional photoresist is a chemically amplified photoresist (CAR), which contains a polymer resin, a photo-acid generator (PAG), and a base (quencher).

[0003] Recently, the semiconductor industry has introduced extreme ultraviolet (EUV) exposure technology (photolithography) that uses an EUV light source, which is capable of forming ultra-fine patterns of 10 nm or less.

[0004] However, EUV has a photon density that is 1 / 14 that of 193nm DUV (deep UV), which can cause stochastic failure, specifically chemical stochastic failure. For example, in the case of CAR, the low photon density reduces the probability of PAG reaction, which can result in 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 are 4nm or larger. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, the problem to be solved by the present invention is to provide a photoresist that has excellent photon absorption and low line edge roughness.

[0006] The technical problems of the present invention are not limited to the technical problems 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, which includes a plurality of molecular beams extending upwardly and laterally from a substrate, each of which is formed by bonding a plurality of inorganic monomolecules with organic monomolecules interposed between at least some of the inorganic monomolecules.

[0008] Van der Waals interactions may exist between the organic monomolecules in laterally adjacent ones of the molecular beams, and the van der Waals interactions may be π-π bonds.

[0009] Each of the molecular beams may be formed by alternately stacking and bonding the inorganic monomolecules and the organic monomolecules.

[0010] The inorganic monomolecules provided on the molecular beam may be arranged uniformly in the horizontal direction to form an inorganic monomolecular layer, and the inorganic monomolecules provided on the molecular beam may be arranged uniformly in the horizontal direction to form an organic monomolecular layer.

[0011] The multilayer molecular film photoresist may have at least one layer selected from the group consisting of a light-absorbing layer having a light-absorbing inorganic monolayer, a photo-reactive layer having a photo-reactive inorganic monolayer, and an etching-resistant layer having an etching-resistant inorganic monolayer. The light-absorbing inorganic monolayer may be an inorganic monolayer having a metal element with a d-orbital. The metal element in the light-absorbing inorganic monolayer may be Sn, Sb, Te, or Bi. The photo-reactive inorganic monolayer may have a metal element selected from Zr, Al, Hf, Zn, and In. The etching-resistant inorganic monolayer may have a metal element selected from Al, Ti, W, Zn, and Cu.

[0012] According to one embodiment of the present invention, there is provided another example of a multilayer molecular film photoresist. The multilayer molecular film photoresist includes a plurality of molecular beams arranged laterally and extending upwardly of a substrate. Each molecular beam has a layer represented by the following Chemical Formula 1:

[0013] [ka] In the above 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, M is an inorganic monomer containing a metal element, O is an organic monomer, m is 1 to 2, n is 1 to 2, and l is 1 to 1000. The organic monomer can be represented by the following formula 3.

[0014] [ka] In the formula 3, 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; X bis 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 C1 to C18 substituted or unsubstituted, linear or branched alkylene group, when MR is the aromatic ring, Z3 and Z4 are, independently of each other, a bond or a C1 to C5 substituted or unsubstituted, linear or branched alkylene group, when MR is the alkylene group, Z3 and Z4 are bonds.

[0015] In Formula 1, M 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.

[0016] The layer represented by Chemical Formula 1 may be a layer represented by Chemical Formula 1A below.

[0017] [ka] In Chemical Formula 1A, 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; M1 is a light-absorbing inorganic monomer containing a metal element having a d orbital; O1 is an organic monomer; m1 may be 1 to 2; n1 may be 1 to 2; and l1 may be 1 to 1000.

[0018] Each of the molecular beams may have a layer represented by the following Chemical Formula 1B above or below the layer represented by the Chemical Formula 1A.

[0019] [ka] In Chemical Formula 1B, 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; M2 is a photoreactive inorganic monolayer including Zr, Al, Hf, Zn, or In; O2 is an organic monolayer; m2 is 1 to 2; n2 is 1 to 2; and l2 is 1 to 1,000.

[0020] Each of the molecular beams may have a layer represented by the following Chemical Formula 1C above or below the layer represented by the Chemical Formula 1A.

[0021] [ka] In Chemical Formula 1C, 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; M3 is an etching-resistant inorganic monolayer including Al, Ti, Cu, W, or Zn; O3 is an organic monolayer; m3 is 1 to 2; n3 is 1 to 2; and l3 is 1 to 1,000.

[0022] The multilayer molecular film photoresist may be an EUV photoresist.

[0023] According to another embodiment of the present invention, there is provided a multilayer molecular film photoresist deposition apparatus, which includes a plurality of molecular beams arranged laterally and extending upwardly of a substrate, each of which produces a multilayer molecular film photoresist having a layer represented by the following Chemical Formula 1, and the layer represented by Chemical Formula 1 is formed by performing a cycle including a step of forming a metal monolayer on the substrate and a step of forming an organic monolayer multiple times:

[0024] [ka] In Chemical Formula 1, 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, M is an inorganic monomer containing a metal element, O is an organic monomer, m is 1 to 2, n is 1 to 2, and l is 1 to 1000. The organic monomer can be represented by Chemical Formula 3 below.

[0025] [ka] In the formula 3, 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; X 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 C1 to C18 substituted or unsubstituted, linear or branched alkylene group, when MR is the aromatic ring, Z3 and Z4 are, independently of each other, a bond or a C1 to C5 substituted or unsubstituted, linear or branched alkylene group, when MR is the alkylene group, Z3 and Z4 are bonds.

[0026] In Formula 1, M 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. [Effects of the Invention]

[0027] The multilayer molecular film photoresist according to one embodiment of the present invention can achieve a very low line edge roughness (LER), which refers to the side roughness of a pattern, of 1.2 nm or less by separating non-particle molecular beams during exposure and development, and can also significantly improve resolution to 6 nm or less.

[0028] In addition, the multilayer molecular film photoresist, in one example, contains an inorganic atom with a very high light absorption rate against EUV, specifically, a light-absorbing inorganic monolayer having a metal atom with a 4d or 5d orbital, 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. [Brief explanation of the drawings]

[0029] [Figure 1]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. [Figure 2] FIG. 2 is a schematic view showing another example of a light absorption layer in 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 illustrating the steps of a photolithography method according to one embodiment of the present invention. [Figure 4] FIG. 4 is a schematic diagram illustrating the steps of a photolithography method according to one embodiment of the present invention. [Figure 5] FIG. 5 is a schematic diagram illustrating the steps of a photolithography method according to one embodiment of the present invention. [Figure 6] FIG. 6 is a schematic diagram illustrating the steps of a photolithography method according to one embodiment of the present invention. [Figure 7] FIG. 7 is a schematic diagram illustrating the steps of a photolithography method according to one embodiment of the present invention. [Figure 8] FIG. 8 shows a unit cycle configuration for forming an inorganic molecular layer. [Figure 9] FIG. 9 is an SEM image taken after patterning the vertically designed inorganic multilayer molecular photoresist formed with reference to FIG. [Figure 10] FIG. 10 shows a unit cycle configuration for forming a multilayer molecular film photoresist having a vertical molecular beam structure. [Figure 11a] FIG. 11a is an SEM image taken after patterning the photoresist formed using the method described with reference to FIG. [Figure 11b] FIG. 11b is an SEM image taken after patterning the photoresist formed using the method described with reference to FIG. [Figure 11c] FIG. 11c is an SEM image taken after patterning the photoresist formed using the method described with reference to FIG. [Figure 12]FIG. 12 is a graph showing the electron beam sensitivity of a photoresist formed using the method described with reference to FIG. [Figure 13a] FIG. 13a is a schematic diagram showing the form and dose conditions for EUV irradiation. [Figure 13b] FIG. 13b is an optical photograph of the photoresist pattern obtained when EUV, as shown in FIG. 13a, is irradiated onto a photoresist using a Hf precursor formed using the method described with reference to FIG. 10. [Figure 14a] FIG. 14a is an atomic force microscopy (AFM) image obtained after electron beam exposure and development of a photoresist using a Zn precursor formed using the method described with reference to FIG. [Figure 14b] FIG. 14b is an atomic force microscopy (AFM) image obtained after electron beam exposure and development of the PMMA photoresist. DETAILED DESCRIPTION OF THE INVENTION

[0030] In this specification, the term "metal" may be a concept that includes all metals, but as an example, the metal may be a transition metal, a post-transition metal, or a metalloid.

[0031] In this specification, the radiation may be, for example, EUV or E-beam, but may also be, but is not limited to, these in some cases.

[0032] In this specification, a single molecule refers to a molecule that is not a polymer, and as an example, refers to a small molecule, specifically a molecule having 100 atoms or less, more specifically a molecule having 30 atoms or less.

[0033] 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.

[0034] In this specification, when it is stated that "carbon number (C)X to carbon number (C)Y" is used, it should be understood that it also describes cases where the carbon number is any integer between carbon number X and carbon number 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.

[0035] In this specification, when "X to Y" is stated, it should be understood that all integers between X and Y are also stated. For example, when it is stated as 1 to 10, it should be understood that 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 are all stated.

[0036] 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.

[0037] 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 the bare substrate on which the element is formed.

[0038] An etching layer 20 may be formed on the substrate 10. The etching layer 20 is a layer that is etched using a photoresist pattern as an etching mask after forming a photoresist pattern to form a pattern, and may be formed of various materials used in semiconductor processes. For example, the etching layer 20 may be a metal film, a semiconductor film, an insulating film, or a composite film containing any one of these. The metal film is used to form wiring and may be aluminum, tungsten, titanium, or a composite film containing any one of these. The semiconductor film may be a silicon film, e.g., single-crystal silicon, polysilicon, amorphous silicon film, or a composite film containing any one 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 one of these. For example, the etching layer 20 may be a bare substrate.

[0039] The surface functional group of the layer to be etched 20 may be, 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.

[0040] A multilayer molecular film photoresist 30 having a molecular beam structure can be formed on the etching target layer 20 .

[0041] The multilayer molecular film photoresist 30 may have a plurality of molecular beams ML extending laterally, each of which is formed by a direct or indirect bond between inorganic monomolecules (M1, M2, or M3). In this case, "indirectly linked" means that another monomolecule, such as an organic monomolecule O1, O2, or O3 (described below), or a functional group is bonded between the inorganic monomolecules M1, M2, or M3. The bond may be a covalent bond or a coordinate bond. In one example, the molecular beams 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.

[0042] In this embodiment, the multilayer molecular film photoresist 30 is formed using atomic layer deposition or molecular layer deposition, so that almost all of the molecular beams ML in the multilayer molecular film photoresist 30 can have substantially the same layered structure. As a result, the molecular beams ML in the multilayer molecular film photoresist 30 can have the same inorganic monolayers and the same organic monolayers in the lateral direction. In other words, the inorganic monomolecules provided in the molecular beams can be arranged in the same lateral direction to form an inorganic monolayer, and the organic monomolecules provided in the molecular beams can be arranged in the same lateral direction to form an organic monolayer.

[0043] The multilayer molecular photoresist 30 may be an organic / inorganic multilayer molecular photoresist. Specifically, the multilayer molecular photoresist 30 refers to a molecular beam ML in which some inorganic monomolecules M1, M2, and M3 are bonded to each other through organic monomolecules O1, O2, and O3. In this case, the multilayer molecular photoresist 30 may include 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 may have van der Waals interactions VI between them. In this case, the van der Waals interactions VI may stabilize adjacent molecular beams ML in the horizontal direction, preventing pattern collapse even when the pattern has a high aspect ratio. For example, the van der Waals interactions may be π-π bonds between aromatic groups.

[0044] The multilayer molecular film photoresist 30 may have a layer structure represented by the following Chemical Formula 1.

[0045] [ka] In Chemical 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. OM may be an organic monolayer. Specifically, OM may be an organic monolayer represented by Chemical Formula 3 below. In Chemical 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, and more specifically 25 to 100. Specifically, m may be 1 to 2, for example, m may be 1. n may also be 1 to 2, for example, n may be 1.

[0046] The MM may be an inorganic monolayer containing a metal element, specifically an organometallic monolayer. For example, the MM may be a light-absorbing inorganic monolayer containing a metal element 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, or Zn. The metal element with 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. The MM may be an organometallic monolayer represented by the following formula 2, specifically, formula 2A, 2B, or 2B:

[0047] [ka] In Formula 2, 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. Z1 and Z2 may be, independently of each other, a 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. M 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 can be O, S, Se, NR (R is H or CH3), or PR (R is H or CH3).

[0048] L a and L b is M 0 The sum of the numbers of ligands, na and nb, is M 0 For example, the sum of na and nb can be an integer between 1 and 4. a and L bmay be, independently of each other, 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, in the above Chemical Formula 2, when na and / or nb are 2 or more, L a and / or L b can be selected from the above examples without regard to each other. 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 M 0 and L can be combined 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, independent of each other.

[0049] 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 type of inorganic monolayer, specifically, organometallic monolayer. The classification of each layer refers to its main function, and all layers may generate secondary electrons through light absorption and perform the photoreaction described below. In one 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.

[0050] The light absorbing layer FL1 may be a layer that has excellent radiation absorption, specifically, EUV or E-beam absorption, and can absorb radiation to generate secondary electrons. The light absorbing layer FL1 may have a layer structure represented by the following Chemical Formula 1A.

[0051] [ka] In Chemical Formula 1A, 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. M1 may be a light-absorbing inorganic monolayer, for example, an organometallic monolayer containing a metal element having a d orbital, specifically a 4d or 5d orbital, such as Sn, Sb, Te, or Bi, and O1 may be an organic monolayer. Furthermore, m1 may be 0 to 10, n1 may be 1 to 10, and l1 may be 1 to 1000. Specifically, m1 may be 1 to 2, for example, m1 may be 1. n1 may also be 1 to 2, for example, n1 may be 1. The light-absorbing inorganic monolayer M1 may be a light-absorbing organometallic monolayer represented by the following chemical formula 2A. In the chemical formula 1A, when n1 is 2 or more or l1 is 2 or more, the light-absorbing inorganic monolayers M1 in each layer may be the same or different.

[0052] [ka] In Formula 2A, 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. Z1 and Z2 may be, independently of each other, a 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. M a X may be an inorganic atom with excellent radiation absorption, specifically EUV or E-beam absorption, for example, a metal atom having a d orbital, for example, a 4d or 5d orbital. The metal atom may be Sn, Bi, Sb, or Te. a can be O, S, Se, NR (R is H or CH3), or PR (R is H or CH3).

[0053] In the formula 2A, L1 and L2 are each M a The sum of n1 and n2, which are the numbers of ligands bound to M aThe coordination number can be determined by the coordination number resulting from the above formula. For example, the sum of n1 and n2 can be an integer from 1 to 4. L1 and L2 can be, independently of each other, 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 can be substituted or unsubstituted, and linear or branched. Also, in Chemical Formula 2A, when n1 and / or n2 are 2 or greater, L1 and / or L2 can be selected, independently of each other, from the above examples. In one example, if the sum of n1 and n2 is 2 or more, two of L1 and L2 are attached to the M a and can combine to form a heterocyclyl or heteroaryl. Z1, Z2, L1, or L2 and M a Each bond between may be a covalent bond or a coordinate bond, independent of each other.

[0054] The organic monolayer O1 may be represented by the following formula 3. In formula 1A, when m1 is 2 or more or l1 is 2 or more, the organic monolayers O1 in each layer may be the same or different.

[0055] [ka] In Formula 3, one of the *'s may be a bond with a functional group in the lower layer or a functional group in the lower monolayer, and the other may be a bond with 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. X b can be O, S, Se, NR (R is H or CH3), or PR (R is H or CH3).

[0056] In one example, M R in Formula 3 may be a substituted or unsubstituted aromatic ring. The substitution may involve the replacement of hydrogen atoms in the aromatic ring with various functional groups. When M R is an aromatic ring, Z and Z may be, independently of each other, a bond or a C1-C5 substituted or unsubstituted, linear or branched alkylene group. The substitution may involve the replacement of hydrogen atoms in the alkylene group with OH, SH, SeH, NR (where R is, independently of each other, H or CH), or PR (where R is, independently of each other, H or CH).

[0057] In another example, M R in Formula 3 may be a C1-C18 substituted or unsubstituted, linear or branched alkylene group. Substitution refers to substitution of hydrogen atoms of the alkylene group with a functional group capable of crosslinking by radiation, for example, a vinyl group, or with OH, SH, SeH, NR2 (R is independently H or CH3), or PR2 (R is independently H or CH3). When M R is an alkylene group, Z3 and Z4 may be a bond.

[0058] The multilayer molecular film photoresist 30 may further include a photoreactive layer FL2 in addition to the light absorbing layer FL1. The photoreactive layer FL2 may have a layer structure represented by the following Chemical Formula 1B.

[0059] [ka] In Chemical Formula 1B, 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. Here, the bond may be, for example, a covalent bond. M2 is a photoreactive inorganic monolayer, for example, an organometallic monolayer including Zr, Al, Hf, Zn, or In, and O2 may be an organic monolayer. Furthermore, m2 may be 0 to 10, n2 may be 1 to 10, and l2 may be 1 to 1000. Specifically, m2 may be 1 to 2, for example, m2 may be 1. n2 may also be 1 to 2, for example, n2 may be 1.

[0060] The photoreactive inorganic monomolecules M2 may be photoreactive organometallic monomolecules represented by the following chemical formula 2B. In the chemical formula 2B, when n2 is 2 or more or l2 is 2 or more, the photoreactive inorganic monomolecules M2 in each layer may be the same or different.

[0061] [ka] In Formula 2B, 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. Here, the bond may be, for example, a covalent bond. Z1 and Z2 may each independently be a 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. M b is a metal atom, and specifically may be Zr, Al, Hf, Zn, or In. X acan be O, S, Se, NR (R is H or CH3), or PR (R is H or CH3).

[0062] L3 and L4 are M b The sum of n1 and n2, which are the numbers of ligands bound to M b The coordination number can be determined by the coordination number resulting from the above formula. For example, the sum of n1 and n2 can be an integer of 1 to 4. L3 and L4 can be, independently of each other, 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 can be a substituted or unsubstituted, linear or branched alkyl group. Furthermore, in Formula 2B, when n1 and / or n2 are 2 or greater, L3 and / or L4 can be selected, independently of each other, from the above examples. In one example, when the sum of n1 and n2 is 2 or greater, two of L3 and L4 can be selected from the M to which they are attached. b and can combine to form a heterocyclyl or heteroaryl. Z1, Z2, L3, or L4 and M b Each bond between may be a covalent bond or a coordinate bond, independent of each other.

[0063] The organic monomolecule O2 can be represented by the above-mentioned Chemical Formula 3. However, it may be the same as or different from the organic monomolecule O1 in the light-absorbing layer FL1, and when m2 is 2 or more or l2 is 2 or more in the above-mentioned Chemical Formula 1B, the organic monomolecule O2 in each layer may be the same as or different from each other.

[0064] Secondary electrons generated in the light absorbing layer FL1 or secondary electrons generated by the metal contained in the photoreactive inorganic monomolecules M2 and / or the etching-resistant inorganic monomolecules M3 described below can form cross-links between adjacent photoreactive inorganic monomolecules M2 in the molecular beam ML. Specifically, the M between adjacent photoreactive inorganic monomolecules M2 can be formed. b-L4 and L3-M b The bond reacts with the secondary electrons to form M b -Y2-M b Such M b -Y2-M b The bond may not be etched by a developing agent, such as a developing gas or plasma, that develops the multilayer molecular film photoresist pattern formed by exposure. b can be selected as above, where Y2 can be O, S, Se, N, or P.

[0065] However, the present invention is not limited to this, and secondary electrons generated in the light-absorbing layer FL1 can also form cross-links between adjacent light-absorbing inorganic monomolecules M1 in the molecular beam ML. Specifically, the M between the adjacent light-absorbing inorganic monomolecules M1 can be formed. a -L2 and L1-M a The bond reacts with the secondary electrons to form M a -Y1-M a A bond can be formed, which also does not need to be etched by the developing agent, where Y1 can be O, S, Se, N, or P.

[0066] The multilayer molecular film photoresist 30 may further include an etching-resistant layer FL3 in addition to the light-absorbing layer FL1. The etching-resistant layer FL3 may have a layer structure represented by the following Chemical Formula 1C.

[0067] [ka] In Chemical Formula 1C, 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. Here, the bond may be, for example, a covalent bond. M3 may be an etching-resistant inorganic monolayer, for example, an organometallic monolayer containing Al, Ti, Cu, W, or Zn, and O3 may be an organic monolayer. Furthermore, m3 may be 0 to 10, n3 may be 1 to 10, and l3 may be 1 to 1000. Specifically, m3 may be 1 to 2, for example, m3 may be 1. Furthermore, n3 may be 1 to 2, for example, n3 may be 1.

[0068] The etching-resistant inorganic monolayer M3 may be an etching-resistant organometallic monolayer represented by the following chemical formula 2C. In the chemical formula 1C, when n3 is 2 or more or l3 is 2 or more, the etching-resistant inorganic monolayers M3 in each layer may be the same or different.

[0069] [ka] In Formula 2C, 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. Here, the bond may be, for example, a covalent bond. Z1 and Z2 may each independently be a 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. M c is a metal atom, and specifically may be Al, Ti, W, Zn, or Cu. X acan be O, S, Se, NR (R is H or CH3), or PR (R is H or CH3).

[0070] L5 and L6 are M c The sum of n1 and n2, which are the numbers of ligands bound to M c The coordination number can be determined by the coordination number resulting from the above formula. For example, the sum of n1 and n2 can be an integer of 1 to 4. L5 and L6 can be, independently of each other, 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 can be a substituted or unsubstituted, linear or branched alkyl group. Furthermore, in Formula 2C, when n1 and / or n2 are 2 or greater, L5 and / or L6 can be selected independently from the above examples. In one example, when the sum of n1 and n2 is 2 or greater, two of L5 and L6 can be selected from the M to which they are attached. c and can combine to form a heterocyclyl or heteroaryl. Z1, Z2, L5, or L6 and M c Each bond between may be a covalent bond or a coordinate bond, independent of each other.

[0071] The organic monolayer O3 can be represented by Chemical Formula 3. The organic monolayer O3 may be the same as or different from the organic monolayer O3 in the light-absorbing layer FL1 or the organic monolayer O2 in the photoreactive layer FL2. When m3 is 2 or greater or l3 is 2 or greater in Chemical Formula 1C, the organic monolayers O3 in each layer may be the same as or different from each other.

[0072] Secondary electrons generated in the light absorbing layer FL1 or secondary electrons generated by the metal contained in the photoreactive inorganic monomolecules M2 and / or the etching-resistant inorganic monomolecules M3 can form cross-links between adjacent etching-resistant inorganic monomolecules M3 in the molecular beam ML. c -L5 or M c The -L6 bond reacts with the secondary electrons to form M c -Y3-M c Such M c -Y 3 -M c The bond may not be etched by the developing agent, and may not be etched by the etching agent, such as plasma, that etches the etching target layer 20. c where Y3 can be O, S, Se, N, or P.

[0073] FIG. 2 is a schematic view showing another example of a light absorption layer in a multilayer molecular film photoresist having a vertical molecular beam structure according to an embodiment of the present invention.

[0074] The light-absorbing layer FL1 shown in Figure 2 corresponds to the case where m1, n1, and l1 in Figure 1 are 1, 1, and 2. Although the light-absorbing layer FL1 is illustrated as an example in Figure 2, the light-reactive layer FL2 and / or the etching-resistant layer FL3 in Figure 1 may also have one of these example structures.

[0075] In Formula 1, 1A, 1B, or 1C, when m, m1, m2, m3, and n, n1, n2, and n3 are all 1, the multilayer molecular film photoresist 30 may have a structure in which inorganic monomolecules MM, M1, M2, or M3 and organic monomolecules OM, O1, O2, or O3 are alternately stacked. In this case, organic monomolecules OM, O1, O2, or O3 are disposed between the inorganic monomolecules MM, M1, M2, or M3, and the inorganic monomolecules MM, M1, M2, or M3 and the organic monomolecules OM, O1, O2, or O3 may all self-assemble in the lower (monolayer) layer. As a result, the molecular beams ML may extend upward, for example, vertically, relative to the substrate 10 while being spaced apart from each other.

[0076] 3 to 7 are schematic diagrams sequentially illustrating a photolithography method according to one embodiment of the present invention. For ease of explanation, FIGS. 3 to 7 exemplarily illustrate a multilayer molecular film photoresist 30 in which n1, n2, n3, m1, m2, m3, l1, l2, and l3 in FIG. 1 are all 1, and exemplarily illustrate a case in which Z1 and Z2 are all bonds and n1 and n2 are all 1 in chemical formulas 2A, 2B, and 2C representing inorganic monomolecules M1, M2, and M3.

[0077] 3, a substrate 10 may be provided on which a layer to be etched 20 is formed. The substrate 10 and the layer to be etched 20 may be the same as those described with reference to FIG.

[0078] A multilayer molecular film photoresist 30 may be formed on the etching target layer 20. The multilayer molecular film photoresist 30 may be the same as the embodiment described with reference to FIG. 1, except as described below. In one embodiment, the multilayer molecular film photoresist 30 is illustrated as having an etching-resistant layer FL3, a light-absorbing layer FL1, and a photoreactive layer FL2 stacked in this order, but is not limited thereto. The stacking order may vary depending on the type of the etching target layer 20 and / or the type of pattern to be formed through photolithography. The multilayer molecular film photoresist 30 may be formed using atomic layer deposition equipment or molecular layer deposition equipment.

[0079] For example, a light absorbing layer FL1 may be formed on the etching target layer 20. The light absorbing layer FL1 may be formed by atomic layer deposition, specifically, molecular layer deposition.

[0080] In one example, the light-absorbing layer FL1 may be formed by performing a cycle including a step of forming a light-absorbing metal monolayer M1 and a step of forming an organic molecular layer O1 multiple times (11 in Chemical Formula 1A). In the step of forming the organic molecular layer O1, a unit cycle may be performed including an organic precursor dosing step in which an organic precursor is dosed and chemically bonded to the lower layer in a self-assembly manner; and a purge step in which a purge gas is supplied to purge unreacted organic precursors and reaction products.

[0081] Here, the purge gas can be argon.

[0082] The organic precursor may be represented by the following Chemical Formula 4:

[0083] [ka] In the above formula 4, R a1 and R a2 may be, independently of each other, hydrogen or a C1-C2 alkyl group, and X b and X a may be, independently of one another, O, S, Se, NR (R is H or CH), or PR (R is H or CH), where Z, Z, and MR are as defined in Formula 3 above.

[0084] Specific examples of the organic precursor are as follows:

[0085] [ka]

[0086] [ka]

[0087] [ka] In the organic precursor dosing step, a reaction according to the following Reaction Scheme 1 may occur.

[0088] [ka] In Reaction Scheme 1, R0 is a functional group on the surface of the lower layer, and R0 can be hydrogen, a hydroxyl 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. a1 X b -Z3-MR-Z4-X a R a2 is an organic precursor, and each functional group is as defined in Chemical Formula 4 above.

[0089] 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 produced as a reaction by-product. A subsequent purge step can purge away any remaining organic precursor and said reaction by-products.

[0090] In the step of forming the light-absorbing metal monolayer M1, a unit cycle can be performed, including a metal precursor dosing step in which a metal precursor is dosed and chemically bonded to the lower layer in a self-assembly manner, and a purge step in which a purge gas is supplied to purge unreacted metal precursor and reaction products, where the purge gas can be argon.

[0091] The metal precursor for forming the light-absorbing metal monolayer M1 can be represented by the following Chemical Formula 5A.

[0092] [ka] In the above formula 5A, R b1 and R b2 may be, independently of each other, 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, L1, L2, n1, n2, and M a is as defined in Formula 2A. In addition, in some cases, R b1 , R b2 , L1, and L2 are directly or indirectly linked to M a and R can be joined to form a heterocyclyl or heteroaryl. b1 and R b2 At least one of the a It may be coordinated to

[0093] Specific examples of metal precursors for forming the light-absorbing metal monolayer M1 are as follows:

[0094] [ka]

[0095] [ka] In the metal precursor, R1, R2, R3, and R4 may be, independently of one another, a C1 to C5 alkyl group.

[0096] In the metal precursor dosing step, a reaction according to the following Reaction Scheme 2 may occur.

[0097] [ka] In the reaction formula 2, *-X a R a2 is the surface functional group of the lower layer, specifically, the surface functional group of the organic molecular layer O1 formed above, and the metal precursor of Chemical Formula 5A can react with the surface functional group of the organic molecular layer O1 formed above to self-assemble on the surface of the organic molecular layer O1. In this process, R a2 R b1 may be produced as a reaction by-product. The remaining metal precursor and the reaction by-products can then be purged in a purge step. In Reaction Scheme 2, each functional group may be the same as defined in Chemical Formula 4 and Chemical Formula 5A.

[0098] Unlike the illustrated example, if the light-absorbing layer FL1 is formed of multiple metal monolayers M1 (i.e., n1 in Formula 1A is 2 or greater), a unit cycle can be repeated, including a reactant gas dosing step in which a reactant gas is dosing to react with the metal precursor chemically bonded to the lower layer, and a purge step in which a purge gas is supplied to purge unreacted reactant gas and reaction products. The reactant gas can be hydrogen, an oxygen-containing gas (e.g., O2, O3, HO), a nitrogen-containing gas (e.g., NH3), etc., after the metal precursor dosing step and purging step according to Reaction Scheme 2 described above.

[0099] A photoreactive layer FL2 may be formed on the substrate on or before the photoabsorption layer FL1 is formed, and the photoreactive layer FL2 may be formed by atomic layer deposition, specifically, molecular layer deposition.

[0100] For example, the photoreactive layer FL2 may be formed by performing a cycle including a step of forming a photoreactive metal monolayer M2 and a step of forming an organic molecular layer O2. The step of forming the organic molecular layer O2 may be performed using the same or similar method as the method of forming the organic molecular layer O1 described for the light-absorbing layer FL1. However, in the organic precursor dosing step of Reaction Scheme 1, -R0 is the terminal group of the metal precursor self-assembled on the underlayer described in Reaction Scheme 2. b2 The step of forming the photoreacted metal monolayer M2 may be performed in a unit cycle including a metal precursor dosing step of dosing a metal precursor and chemically bonding the metal precursor to the underlayer in a self-assembly manner, and a purge step of supplying a purge gas to purge unreacted metal precursor and reaction products. Here, the purge gas may be argon.

[0101] The metal precursor for forming the photoreactive metal monolayer M2 can be represented by the following Chemical Formula 5B.

[0102] [ka] In the above formula 5B, 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, L3, L4, n1, n2, and M b is as defined in Formula 2B. In addition, in some cases, R b1 , R b2 Two of R, L, and L can be bonded directly or indirectly to Mb to form a heterocyclyl or heteroaryl. b1 and R b2 At least one of theb It may be coordinated to

[0103] Specific examples of metal precursors for forming the photoreactive metal monolayer M2 are as follows:

[0104] [ka] In the metal precursor dosing step, a reaction according to the following Reaction Scheme 3 may occur.

[0105] [ka] In the reaction formula 3, *-X a R a2 is the surface functional group of the lower layer, specifically, the surface functional group of the organic molecular layer O2 formed above, and the metal precursor of Chemical Formula 5B can react with the surface functional group of the organic molecular layer O2 formed above to self-assemble on the surface of the organic molecular layer O2. In this process, R a2 R b1 may be produced as a reaction by-product. The remaining metal precursor and the reaction by-products can then be purged in a purge step. In Reaction Scheme 3, each functional group may be the same as defined in Chemical Formula 4 and Chemical Formula 5B.

[0106] Unlike the illustrated example, if the photoreactive layer FL1 is formed of multiple metal monolayers M2 (i.e., n2 in Formula 1B is 2 or greater), a unit cycle can be repeated, including a reactant gas dosing step in which a reactant gas is dosing to react with the metal precursor chemically bonded to the lower layer, and a purge step in which a purge gas is supplied to purge unreacted reactant gas and reaction products. The reactant gas can be hydrogen, an oxygen-containing gas (e.g., O2, O3, HO), a nitrogen-containing gas (e.g., NH3), etc., after the metal precursor dosing step and purging step according to Reaction Scheme 3 described above.

[0107] An etching-resistant layer FL3 may be formed on the substrate on or before the light-absorbing layer FL1 is formed, and the etching-resistant layer FL3 may be formed by atomic layer deposition, specifically, molecular layer deposition.

[0108] For example, the etching-resistant layer FL3 may be formed by performing a cycle including a step of forming an etching-resistant metal monolayer M3 and a step of forming an organic molecular layer O3. The step of forming the organic molecular layer O3 may be formed using the same or similar method as the method of forming the organic molecular layer O1 described for the light-absorbing layer FL1. However, in the organic precursor dosing step of Reaction Scheme 1, -R0 may be a surface functional group bonded to the surface to be etched.

[0109] The step of forming the etching-resistant metal monolayer M3 may be performed in a unit cycle including a metal precursor dosing step of dosing a metal precursor and chemically bonding the metal precursor to the underlayer in a self-assembly manner, and a purge step of supplying a purge gas to purge unreacted metal precursor and reaction products, where the purge gas may be argon.

[0110] The metal precursor for forming the etching-resistant metal monolayer M3 may be represented by the following Chemical Formula 5C.

[0111] [ka] In the above formula 5C, 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, L5, L6, n1, n2, and M cis as defined in Formula 2C. In addition, in some cases, R b1 , R b2 , L5, and L6 are directly or indirectly linked to M c and R can be joined to form a heterocyclyl or heteroaryl. b1 and R b2 At least one of the c It may be coordinated to

[0112] Specific examples of metal precursors for forming the etching-resistant metal monolayer M3 are as follows:

[0113] [ka] In the metal precursor dosing step, a reaction according to the following Reaction Scheme 4 may occur.

[0114] [ka] In the reaction formula 4, -X a R a2 is the surface functional group of the lower layer, specifically, the surface functional group of the organic molecular layer O3 formed above, and the metal precursor of Formula 5C can react with the surface functional group of the organic molecular layer O3 formed above to self-assemble on the surface of the organic molecular layer O3. In this process, R a2 R b1 may be produced as a reaction by-product. The remaining metal precursor and the reaction by-products can then be purged in a purge step. In Reaction Scheme 4, each functional group may be the same as defined in Chemical Formula 4 and Chemical Formula 5C.

[0115] Unlike the illustrated example, if the etching-resistant layer FL1 is formed of multiple metal monolayers M3 (i.e., n3 in Formula 1C is 2 or greater), a unit cycle can be repeated, including a reactant gas dosing step in which a reactant gas is dosing to react with the metal precursor chemically bonded to the lower layer, and a purge step in which a purge gas is supplied to purge unreacted reactant gas and reaction products. The reactant gas can be hydrogen, an oxygen-containing gas (e.g., O2, O3, HO), a nitrogen-containing gas (e.g., NH3), etc., after the metal precursor dosing step and purging step described above according to Reaction Scheme 4.

[0116] However, without being limited to the above, in another embodiment of the present invention, the multilayer molecular photoresist 30 may be formed by performing 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). The step of forming the organic molecular layer (OM of Chemical Formula 1) may be performed by performing a unit cycle including an organic precursor dosing step of dosing an organic precursor of Chemical Formula 4 and chemically bonding the organic precursor to the lower layer in a self-assembly manner; and a purge step of supplying a purge gas to purge unreacted organic precursor and reaction products. Here, the purge gas may be argon. During the organic precursor dosing step, a reaction according to Reaction Scheme 1 may occur.

[0117] The step of forming the metal monolayer (MM of Chemical Formula 1) may be performed in a unit cycle including a metal precursor dosing step of dosing a metal precursor of Chemical Formula 5 below and chemically bonding the metal precursor to the lower layer in a self-assembly manner; and a purging step of supplying a purge gas to purge unreacted metal precursor and reaction products. Here, the purge gas may be argon.

[0118] [ka] In the above formula 5, R b1 and R b2may be, independently of each other, 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, L a , L b , na, nb, 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 bonded to M 0 and R can be joined to form a heterocyclyl or heteroaryl. b1 and R b2 At least one of the 0 It may be coordinated to

[0119] In the metal precursor dosing step, a reaction according to the following Reaction Scheme 5 may occur.

[0120] [ka] In the reaction formula 5, *-X a R a2 is the surface functional group of the lower layer, specifically, the surface functional group of the organic molecular layer O formed above, and the metal precursor of Chemical Formula 5 can react with the surface functional group of the organic molecular layer O formed above to self-assemble on the surface of the organic molecular layer O. In this process, R a2 R b1 may be produced as a reaction by-product. The remaining metal precursor and the reaction by-product may then be purged in a purge step. In Reaction Scheme 5, each functional group may be the same as defined in Chemical Formulas 4 and 5.

[0121] Specifically, the metal precursor may be represented by Chemical Formula 5A, 5B, or 5C. Specifically, the reaction according to Reaction Formula 2, 3, or 4 may occur in the metal precursor dosing step.

[0122] 4, a portion of the multilayer molecular film photoresist 30 may be irradiated with radiation hv, specifically, EUV or E beam. In this case, M, a metal atom having a d orbital, for example, a 4d or 5d orbital, in the light absorbing layer FL1, may be irradiated with radiation hv, specifically, EUV or E beam. a can absorb the radiation and generate secondary electrons. However, without limitation, metal atoms or other elements in the photoreactive layer FL2 and / or the etching-resistant layer FL3 can also absorb radiation and generate secondary electrons.

[0123] The secondary electrons generated in the light absorbing layer FL1 can form cross-links between the photoreactive inorganic monomolecules M2 in the adjacent molecular beams ML. b -L4 and L3-M b reacts with the secondary electrons to form M b -Y2-M b Here, Y2 can be O, S, Se, N, or P. In addition, secondary electrons generated in the light-absorbing layer FL1 can also form cross-links between light-absorbing inorganic monomolecules M1 in adjacent molecular beams ML. Specifically, M a -L2 and L1-M a The bond reacts with the secondary electrons to form M a -Y1-M a Here, Y1 can be O, S, Se, N, or P. In addition, a cross-linking bond can be formed between adjacent etching-resistant inorganic monomolecules M3 in the molecular beam ML by secondary electrons generated in the light-absorbing layer FL1. Specifically, M c -L6 and L5-M c The bond reacts with the secondary electrons to form M c-Y3-M c A bond can be formed: where Y3 can be O, S, Se, N, or P.

[0124] 5, the multilayer molecular film photoresist 30 exposed to radiation can be exposed to a developing agent. In this case, the inorganic monomolecules M1, M2, and M3 in adjacent molecular beams ML are also removed by the developing agent except for the portions where crosslinks are formed, thereby forming a multilayer molecular film photoresist pattern 31. The developing agent can 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 from any of these.

[0125] 6, the etching target film 20 can be etched using the multilayer molecular film photoresist pattern 31 as a mask. This etching can be, for example, plasma etching. At this time, the M between the etching-resistant inorganic monomolecules M3 c -Y3-M c The bonding increases the etching resistance of the multilayer molecular film photoresist pattern 31, allowing the film 20 to be selectively etched.

[0126] 7, the multilayer molecular film photoresist pattern 31 can be removed by using an ashing method.

[0127] The molecular layer deposition equipment for manufacturing a multilayer molecular film photoresist will be described with further reference to Figure 3. Except as otherwise described below, the description with reference to Figures 1, 2a, 2b, and 3 will be used.

[0128] A molecular layer deposition apparatus according to an embodiment of the present invention can 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. The step of forming the organic molecular layer (OM of Chemical Formula 1) can be performed using a unit cycle including an organic precursor dosing step in which an organic precursor of Chemical Formula 4 is dosing and chemically bonding the organic precursor to the lower layer in a self-assembly manner; and a purge step in which a purge gas is supplied to purge unreacted organic precursor and reaction products. Here, the purge gas can be argon. During the organic precursor dosing step, a reaction according to Reaction Scheme 1 can occur.

[0129] The step of forming the metal monolayer (MM of Chemical Formula 1) may be performed in a unit cycle including a metal precursor dosing step of dosing a metal precursor of Chemical Formula 5 and chemically bonding the metal precursor to the underlayer in a self-assembly manner; and a purge step of supplying a purge gas to purge unreacted metal precursor and reaction products. Here, the purge gas may be argon. The metal precursor dosing step may involve a reaction according to Reaction Scheme 5. Specifically, the metal precursor may be represented by Chemical Formula 5A, 5B, or 5C. Specifically, the metal precursor dosing step may involve a reaction according to Reaction Scheme 2, 3, or 4.

[0130] Specifically, the molecular layer deposition apparatus according to one embodiment of the present invention can form a light-absorbing layer FL1 by performing a cycle including a step of forming a light-absorbing metal monolayer M1 and a step of forming an organic molecular layer O1 on a substrate multiple times, specifically, the number of times indicated by 11 in Chemical Formula 1A.

[0131] In the step of forming the organic molecular layer O1, a unit cycle may be performed including an organic precursor dosing step in which the organic precursor of Formula 4 is dosed and chemically bonded to the lower layer in a self-assembly manner; and a purge step in which a purge gas is supplied to purge unreacted organic precursor and reaction products. Here, the purge gas may be argon. During the organic precursor dosing step, a reaction according to Reaction Scheme 1 may occur.

[0132] The step of forming the light-absorbing metal monolayer M1 may be performed in a unit cycle including a metal precursor dosing step of dosing the metal precursor of Formula 5A and chemically bonding the metal precursor to the underlayer in a self-assembly manner; and a purging step of supplying a purge gas to purge unreacted metal precursor and reaction products. Here, the purge gas may be argon. During the metal precursor dosing step, a reaction according to Reaction Scheme 2 may occur.

[0133] The photoreactive layer FL2 can be formed by repeating a cycle including forming a photoreactive metal monolayer M2 and an organic molecular layer O2 on the substrate multiple times, specifically, the number of times indicated by 12 in Formula 1B, on or before the light absorbing layer FL1 is formed. The step of forming the organic molecular layer O2 can be formed using the same or similar method as described for the light absorbing layer FL1.

[0134] The step of forming the photoreactive metal monolayer M2 may be performed in a unit cycle including a metal precursor dosing step of dosing the metal precursor of Formula 5B and chemically bonding the metal precursor to the underlayer in a self-assembly manner; and a purge step of supplying a purge gas to purge unreacted metal precursor and reaction products. Here, the purge gas may be argon. During the metal precursor dosing step, a reaction according to Reaction Scheme 3 may occur.

[0135] The etching-resistant layer FL3 may be formed by repeating a cycle including forming an etching-resistant metal monolayer M3 and an organic molecular layer O3 on the substrate multiple times, specifically, the number of times indicated by 13 in Formula 1C, on or before the light-absorbing layer FL1 is formed. The step of forming the organic molecular layer O3 may be performed using the same or similar method as described for the light-absorbing layer FL1.

[0136] The step of forming the etching-resistant metal monolayer M3 may be performed in a unit cycle including a metal precursor dosing step of dosing a metal precursor of Formula 5C and chemically bonding the metal precursor to the underlayer in a self-assembly manner; and a purge step of supplying a purge gas to purge unreacted metal precursor and reaction products. Here, the purge gas may be argon. During the metal precursor dosing step, a reaction according to Reaction Scheme 4 may occur.

[0137] As described above, in the multilayer molecular film photoresist 30 according to an embodiment of the present invention, the inorganic and organic monomolecules connected by bonds within the molecular beams are formed by self-assembly, so that each molecular beam can grow upward toward the substrate and can be uniformly arranged in the lateral direction.

[0138] In this case, the spacing between the molecular beams (D in FIG. 1 or FIG. 4) is very small, less than 1 nm, specifically less than 0.5 nm. Furthermore, by separating the non-particle molecular beams during exposure and development, the line edge roughness (LER), which refers to the roughness of the pattern side surface, is very low, less than 1.2 nm, and the resolution can be significantly improved to less than 6 nm. Additionally, the multilayer molecular film photoresist 30 contains a light-absorbing inorganic single molecule M1 having an inorganic atom with a very high light absorption rate for EUV, specifically, a metal atom with a 4d or 5d orbital, and has low stochastic failure even for EUV with a low photon density, while also having high photosensitivity (e.g., 10 mJ / cm). 2 ) can be shown.

[0139] In the following, preferred examples are presented to aid in understanding the present invention, but the following examples are merely intended to aid in understanding the present invention and are not intended to limit the scope of the present invention.

[0140] FIG. 8 shows a unit cycle configuration for forming an inorganic molecular layer.

[0141] Referring to FIG. 8, a ZnO inorganic molecular layer was formed by repeating a unit cycle of dosing DEZ (diethylzinc) into the chamber for 2 seconds, purging the chamber for 30 seconds, dosing water (HO) for 2 seconds, and purging the chamber for 30 seconds multiple times (30 times).

[0142] 9 is an SEM image taken after patterning the inorganic multilayer molecular film photoresist with a vertical design formed with reference to FIG. 8. Specifically, a voltage of 100 kV and a current of 2500 uC / cm were applied to the inorganic multilayer molecular film with a vertical design formed with reference to FIG. 2 After irradiation with e-beam under the dose condition, the sample was subjected to ultrasonic treatment in TMAH (tetramethylammonium hydroxide) in H2O for 2 minutes and then decomposed.

[0143] Referring to FIG. 9, it can be seen that patterns having a line width of 1 um and patterns having a line width of 500 nm were clearly formed.

[0144] FIG. 10 shows a unit cycle configuration for forming a multilayer molecular film photoresist having a vertical molecular beam structure.

[0145] Referring to FIG. 10, a substrate was loaded into a chamber, and while the substrate temperature was maintained at 100 to 300°C (specifically, 100 to 150°C), an inorganic precursor such as Hf precursor (Tetrakisdimethylamido Hafnium), Ti precursor (Tetrakisdimethylamido Titanium), Al precursor (Trimethyl Aluminum), or DEZ (Diethylzinc) was dosed at a pressure of 0.01 to 10 torr (0.05 to 0.5 torr) for 1 second, the chamber was purged for 5 seconds, and an organic precursor such as 4-mercaptophenol was dosed at a pressure of 0.01 to 10 torr (0.01 torr) for 1 second, and the chamber was purged for 5 seconds. This unit cycle was repeated multiple times (approximately 30 times) to form a multilayer molecular film photoresist having a thickness of approximately 20 nm.

[0146] 11a, 11b, and 11c are SEM images taken after patterning the photoresist formed using the method described with reference to Fig. 10. Specifically, a voltage of 100 kV, 100 pA, and 2500 uC / cm were applied to the photoresist formed with reference to Fig. 10. 2 After exposure to e-beam under the dose condition, the film was developed by ultrasonic treatment in TMAH (tetramethylammonium hydroxide) in H2O for 2 minutes.

[0147] 11a, 11b, and 11c, a pattern having a line width with a half pitch of 500 nm 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.

[0148] Figure 12 is a graph showing the sensitivity of a photoresist formed using the method described with reference to Figure 10 to an electron beam. Specifically, a voltage of 100 kV, 100 pA, and a sensitivity of 1 to 10,000 uC / cm were applied to the photoresist formed with reference to Figure 10. 2After exposure to e-beam under the dose condition, the pattern was developed by ultrasonic treatment in TMAH (tetramethylammonium hydroxide) in H2O for 2 minutes, and the thickness of the pattern was measured according to the exposure dose.

[0149] Referring to FIG. 12, in this experiment, the normalized thickness of the negative photoresist was expressed as 1 nm if the thickness immediately after deposition was maintained even after development. The multilayer molecular film photoresist formed using the Hf precursor exhibited a normalized thickness of 1 nm at the lowest e-beam dose, indicating that it had the best sensitivity.

[0150] Fig. 13a is a schematic diagram showing the form and dose conditions of EUV irradiation, and Fig. 13b is an optical photograph of a photoresist pattern obtained when EUV as shown in Fig. 13a is irradiated onto a photoresist using a Hf precursor formed by the method described with reference to Fig. 10. Specifically, Fig. 13a is a photograph of a photoresist using a Hf precursor formed with reference to Fig. 10, which is exposed to EUV as shown in Fig. 13a, and then ultrasonically treated in TMAH (tetramethylammonium hydroxide) in HO for 2 minutes, followed by development.

[0151] Referring to Figures 13a and 13b, when a photoresist using a Hf precursor, which is approximately 20 nm thick as deposited, is exposed to EUV, it exhibits a photoresist strength of approximately 40 mJ / cm 2 When exposed to a dose of 40 mJ / cm or more and developed, the thickness is about 10 nm or more. Therefore, the EUV sensitivity of the photoresist using the Hf precursor according to this example is 40 mJ / cm. 2 It can be seen that...

[0152] Figure 14a is an AFM (Atomic Force Microscopy) image obtained after electron beam exposure and development of a photoresist using a Zn precursor formed using the method described with reference to Figure 10, and Figure 14b is an AFM (Atomic Force Microscopy) image obtained after electron beam exposure and development of a PMMA photoresist. In this case, the PMMA photoresist was formed by coating a solution of PMMA dissolved in chlorobenzene, irradiating it with an electron beam, and removing the irradiated portions by development to obtain a pattern. The electron beam irradiated to both photoresists was commonly set at a voltage of 100 kV, 100 pA, and 2500 uC / cm. 2 The photoresist using the Zn precursor was ultrasonically treated in tetramethylammonium hydroxide (TMAH) in H2O for 2 minutes, and the unexposed areas were removed by development.

[0153] Referring to Figures 14a and 14b, it can be seen that the photoresist using the Zn precursor has lower line edge roughness compared to the PMMA photoresist.

Claims

1. A plurality of molecular beams are arranged laterally and each extending upwardly from the substrate, each molecular beam is formed by bonding a large number of inorganic monomolecules with organic monomolecules interposed between at least some of the inorganic monomolecules, A multilayer molecular film photoresist in which crosslinks are formed between the inorganic monomolecules in the molecular beam in the areas irradiated with radiation.

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

3. 3. The multilayer molecular film photoresist according to claim 2, wherein the van der Waals interaction is a π-π bond.

4. 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 fashion.

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

6. The multilayer molecular film photoresist according to claim 5, wherein the multilayer molecular film photoresist has at least one layer selected from the group consisting of a light-absorbing layer comprising a light-absorbing inorganic monolayer, a photoreactive layer comprising a photoreactive inorganic monolayer, and an etching-resistant layer comprising an etching-resistant inorganic monolayer.

7. 7. The multilayer molecular film photoresist according to claim 6, wherein the light-absorbing inorganic monolayer is an inorganic monolayer having a metal element with a d-orbital.

8. 8. The multilayer molecular film photoresist according to claim 7, wherein the metal element is Sn, Sb, Te, or Bi.

9. 7. The multilayer molecular film photoresist according to claim 6, wherein the photoreactive inorganic monolayer is an inorganic monolayer having a metal element selected from the group consisting of Zr, Al, Hf, Zn, and In.

10. 7. The multilayer molecular film photoresist according to claim 6, wherein the etching-resistant inorganic monolayer is an inorganic monolayer having a metal element selected from the group consisting of Al, Ti, W, Zn, and Cu.

11. A plurality of molecular beams are arranged laterally and each extending upwardly from the substrate, Each of the molecular beams has a layer represented by the following chemical formula 1: 【Chemistry 1】 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 monomolecule containing a metal element, OM is an organic monomolecule, m is 1 to 2, n is 1 to 2, and l is 1 to 1000; A multilayer molecular film photoresist in which crosslinks are formed between the inorganic monomolecules in the molecular beam in the areas irradiated with radiation.

12. 12. The multilayer molecular film photoresist of claim 11, wherein the organic monolayer is represented by the following chemical formula 3: 【Chemistry 2】 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 ｂ is O, S, Se, NR (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 or branched alkylene group; When MR is the aromatic ring, Z ３ and Z ４ are, independently of each other, a bond or a C1-C5 substituted or unsubstituted, linear or branched alkylene group, When MR is the alkylene group, Z ３ and Z ４ is a bond.

13. 12. The multilayer molecular film photoresist according to claim 11, wherein M is 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.

14. The multilayer molecular film photoresist according to claim 11, wherein the layer represented by Chemical Formula 1 is a layer represented by the following Chemical Formula 1A: 【Transformation 3】 In Chemical Formula 1A, 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; M1 is a light-absorbing inorganic monolayer containing a metal element with a d orbital; O1 is an organic monolayer, m1 is 1 to 2, n1 is 1 to 2, and l1 is 1 to 1000.

15. 15. The multilayer molecular film photoresist of claim 14, wherein each molecular beam comprises a layer represented by the following Chemical Formula 1B above or below the layer represented by Chemical Formula 1A: 【Chemistry 4】 In Chemical Formula 1B, 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; M2 is a photoreactive inorganic monolayer containing Zr, Al, Hf, Zn, or In; O2 is an organic monomolecule, m2 is 1 to 2, n2 is 1 to 2, and l2 is 1 to 1000.

16. 15. The multilayer molecular film photoresist of claim 14, wherein each molecular beam comprises a layer represented by the following Chemical Formula 1C above or below the layer represented by Chemical Formula 1A: 【Transformation 5】 In Chemical Formula 1C, 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; M3 is an etching-resistant inorganic monolayer containing Al, Ti, Cu, W, or Zn; O3 is an organic monolayer, m3 is 1 to 2, n3 is 1 to 2, and l3 is 1 to 1000.

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

18. A multilayer molecular film photoresist is manufactured by providing a plurality of molecular beams extending upwardly of a substrate and arranged laterally, each of the molecular beams having a layer represented by the following Chemical Formula 1: The layer represented by Formula 1 is formed by repeating a cycle including a step of forming a metal monolayer on a substrate and a step of forming an organic monolayer multiple times. 【Transformation 6】 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 monomolecule containing a metal element, OM is an organic monomolecule, m is 1 to 2, n is 1 to 2, and l is 1 to 1000; The multilayer molecular film photoresist is a multilayer molecular film photoresist deposition device that forms crosslinks between the inorganic monomolecules in the molecular beam at the portions irradiated with radiation.

19. 19. The multilayer molecular film photoresist deposition equipment according to claim 18, wherein M is 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.

20. 19. The multilayer molecular film photoresist deposition equipment of claim 18, wherein the organic monolayer is represented by the following Chemical Formula 3: 【Transformation 7】 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 ｂ is O, S, Se, NR (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 or branched alkylene group; When MR is the aromatic ring, Z ３ and Z ４ are, independently of each other, a bond or a C1-C5 substituted or unsubstituted, linear or branched alkylene group, When MR is the alkylene group, Z ３ and Z ４ is a bond.

21. A process for forming a multilayer molecular film photoresist on a substrate, the multilayer molecular film photoresist comprising a number of molecular beams arranged laterally and each extending upwardly of the substrate, the molecular beams being formed by bonding a number of inorganic monomolecules with organic monomolecules interposed between at least some of the inorganic monomolecules; irradiating a portion of the multilayer molecular film photoresist with radiation; forming cross-links between the inorganic monomolecules in the molecular beam in the irradiated area; and The method for producing a photoresist pattern includes developing the multilayer molecular film photoresist in which crosslinks are formed.

22. The method for manufacturing a photoresist pattern according to claim 21, wherein the radiation is EUV or Ebeam.

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