WO2023018308A1

WO2023018308A1 - Multi-layered molecular film photoresist having molecular line structure and method for manufacturing same

Info

Publication number: WO2023018308A1
Application number: PCT/KR2022/012143
Authority: WO
Inventors: 성명모; 안진호; 박영은; 지현석; 이재혁
Original assignee: 한양대학교 산학협력단
Priority date: 2021-08-12
Filing date: 2022-08-12
Publication date: 2023-02-16

Abstract

A multi-layered molecular film photoresist is provided. The multi-layered molecular film photoresist includes a plurality of molecular lines arranged in a longitudinal direction of a substrate, each of the molecular lines being extended in an upper direction of the substrate. Each of the molecular lines is in a connected state in which a plurality of inorganic single molecules are bonded to organic single molecules each interposed between at least some of the inorganic single molecules.

Description

Multilayer Molecular Film Photoresist with Molecular Line Structure and Manufacturing Method Thereof

The present invention relates to a photoresist, and more particularly to a photoresist for EUV.

Research has been continuously conducted in relation to photoresist, and in particular, a method of preparing a photoresist in a liquid state and then spin-coating it to deposit it on a substrate has been studied most actively. As such a conventional photoresist, a chemically amplified photoresist (CAR) containing a polymer resin, a photo-acid generator (PAG), and a base (quencher) is mainly used.

Recently, the semiconductor industry has introduced EUV photo lithography using an extreme ultraviolet (EUV) light source capable of forming ultra-fine patterns of 10 nm or less.

However, since EUV has a photon density as low as 1/14 of that of 193 nm deep UV (DUV), it may cause stochastic failure, specifically, chemical stochastic failure. For example, in the case of the CAR, shot noise may occur due to a low probability that the PAG responds due to a low photon density. In addition, it is known that in the case of CAR, there is a disadvantage in that the size of the polymer resin particles is larger than 4 nm, resulting in relatively large line edge roughness.

Accordingly, an object to be solved by the present invention is to provide a photoresist having excellent photon absorption and low edge roughness.

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.

According to one embodiment of the present invention, a multilayer molecular film photoresist is provided. The multilayer molecular film photoresist includes a plurality of molecular lines extending in an upper direction of the substrate and arranged in a transverse direction. Each molecular line is formed by bonding a plurality of inorganic single molecules and organic single molecules interposed between at least some of the inorganic single molecules among the inorganic single molecules.

Van der Waals interactions may exist between the organic monomolecules in horizontally adjacent molecular lines among the molecular lines. The van der Waals interaction may be a π-π bond.

Each of the molecular lines may be obtained by alternately stacking and combining the inorganic single molecule and the organic single molecule.

Inorganic monomolecules included in the molecular wires may be equally arranged in a lateral direction to form an inorganic monomolecular layer, and inorganic monomolecules included in the molecular wires may be equally arranged in a lateral direction to constitute an organic monomolecular layer.

The multilayer molecular film photoresist may have at least one of a light absorbing layer including light absorbing inorganic single molecules, a photoreactive layer including photoreactive inorganic single molecules, and an etch resistant layer including etch resistant inorganic single molecules. there is. The light-absorbing inorganic inorganic molecule may be an inorganic inorganic molecule having a metal element having a d orbital. The metal element in the light-absorbing inorganic group molecule may be Sn, Sb, Te, or Bi. The photoreactive inorganic single molecule may have a metal element such as Zr, Al, Hf, Zn, or In. The etch-resistant inorganic single molecule may have a metal element such as Al, Ti, W, Zn, or Cu.

According to one embodiment of the present invention, another example of a multilayer molecular film photoresist is provided. The multilayer molecular film photoresist includes a plurality of molecular lines extending in an upper direction of the substrate and arranged in a transverse direction. Each of the above molecular lines has a layer represented by Formula 1 below.

[Formula 1]

In Formula 1, one of * is a bond with a functional group in the lower layer, the other is a bond with a functional group in the upper layer, M is an inorganic single molecule containing a metal element, O is an organic single molecule, and m is 1 to 2, n is 1 to 2, and l is 1 to 1000.

The organic single molecule may be represented by Formula 3 below.

[Formula 3]

In Formula 3, one of * is a bond with a functional group in the lower layer, the other is a bond with a functional group in the upper layer, and X _b is O, S, Se, NR (R is H or CH ₃ ) or PR ( R is H or CH ₃ ), MR is a substituted or unsubstituted aromatic ring, or a C1 to C18 substituted or unsubstituted linear or branched alkylene group, and when MR is the above aromatic ring, Z ₃ and Z ₄ are, independently of each other, a bond or a C1 to C5 substituted or unsubstituted and linear or branched alkylene group, and when MR is the alkylene group, Z ₃ and Z ₄ are bonds.

In Formula 1, M is a light absorbing inorganic single molecule containing a metal element having d orbital, a photoreactive inorganic single molecule including Zr, Al, Hf, Zn, or In, or Al, Ti, Cu, W, Or it may be an etch-resistant inorganic single molecule containing Zn.

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

[Formula 1A]

In Chemical Formula 1A, one of * 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, M1 is a light-absorbing inorganic monomolecule containing a metal element having a d orbital, and O1 is It is an organic single molecule, m1 may be 1 to 2, n1 may be 1 to 2, and l1 may be 1 to 1000.

Each of the molecular wires may include a layer represented by Chemical Formula 1B below or above the layer represented by Chemical Formula 1A.

[Formula 1B]

In Formula 1B, one of * 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, M2 is a photoreactive inorganic monomolecule including Zr, Al, Hf, Zn, or In, , O2 is an organic monomer, m2 is 1 to 2, n2 is 1 to 2, and l2 may be 1 to 1000.

Each of the molecular lines may include a layer represented by the following Chemical Formula 1C above or below the layer represented by the Chemical Formula 1A.

[Formula 1C]

In Formula 1C, one of * 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 etch-resistant inorganic monomolecule including Al, Ti, Cu, W, and Zn, O3 is an organic monomer, m3 may be 1 to 2, n3 may be 1 to 2, and l3 may be 1 to 1000.

The multilayer molecular film photoresist may be a photoresist for EUV.

According to another embodiment of the present invention, it is possible to provide a multilayer molecular film photoresist deposition equipment. The multilayer molecular film photoresist deposition equipment is provided with a plurality of molecular lines extending in the upper direction of the substrate and arranged in a lateral direction, wherein each molecular line has a layer represented by the following formula (1) To prepare a multilayer molecular film photoresist, The layer represented by Chemical Formula 1 is formed by performing a plurality of cycles including forming a metal monomolecular layer and forming an organic molecular layer on a substrate.

[Formula 1]

The organic single molecule may be represented by Formula 3 below.

[Formula 3]

The multilayer molecular film photoresist according to an embodiment of the present invention has Line Edge Roughness (LER) of 1.2 nm or less, which means pattern side roughness, as it separates between molecular lines rather than particles during exposure and development. It may be low, and also the resolution (resolution) can also be greatly improved to 6 nm or less.

In addition, the multilayer molecular film photoresist includes, in one example, an inorganic atom having a very high light absorption rate for EUV, specifically, a light absorbing inorganic single molecule having a metal atom having a 4d or 5d orbital, and thus having a low photon density for EUV. It can exhibit high photosensitivity (ex. 10 mJ/cm ² ) while having a low stochastic failure.

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

2 is a schematic diagram showing another example of a light absorbing layer in a multilayer molecular film photoresist having a vertical molecular beam structure according to an embodiment of the present invention.

3 to 7 are schematic diagrams sequentially showing a photolithography method according to an embodiment of the present invention.

8 shows a unit cycle configuration for forming an inorganic molecular layer.

Figure 9 is a vertical design formed with reference to Figure 8 This is a SEM image taken after patterning the inorganic multilayer molecular film photoresist.

10 shows a unit cycle configuration for forming a multilayer molecular film photoresist having a vertical molecular line structure.

11A, 11B, and 11C are SEM images taken after patterning the photoresist formed using the method described with reference to FIG. 10 .

FIG. 12 is a graph showing the electron beam sensitivity of a photoresist formed using the method described with reference to FIG. 10 .

FIG. 13a is a schematic diagram showing a form of irradiating EUV and a dose condition, and FIG. 13b is a photoresist obtained when irradiating EUV as shown in FIG. 13a to a photoresist using an Hf precursor formed using the method described with reference to FIG. 10 This is an optical photograph of a photoresist pattern.

FIG. 14a is an atomic force microscopy (AFM) image obtained after electron beam exposure and development of a photoresist using a Zn precursor formed by the method described with reference to FIG. 10, and FIG. 14b is an atomic force microscopy (AFM) image obtained after electron beam exposure and development of a PMMA photoresist. This is an AFM (Atomic force microscopy) image.

In this specification, the metal may be a concept including all metals, but as an example, it may be a transition metal, a post-transition metal, or a metalloid.

In this specification, radiation may be, for example, EUV or E-beam. However, in some cases, it is not limited to this.

In the present specification, a single molecule refers to a molecule other than a polymer, and as an example, a small molecule may refer to a molecule having 100 or less atoms, specifically, 30 or less atoms.

In the present specification, molecules or functional groups "linked by a bond" may mean that they are directly linked or indirectly linked by placing another molecule(s) or functional group therebetween.

In the present specification, when "carbon number (C)X to carbon number (C)Y" is described, it should be interpreted as having a number of carbon atoms corresponding to all integers between carbon number X and carbon number Y. For example, when C1 to C10 are described, it should be interpreted that C1, C2, C3, C4, C5, C6, C7, C8, C9, and C10 are all described.

In this specification, when "X to Y" is described, it should be interpreted that the numbers corresponding to all integers between X and Y are also described. For example, when written as 1 to 10, it should be interpreted that 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 are all described.

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. On the substrate, at least one device (not shown) such as a transistor, memory, diode, solar cell, optical device, biosensor, nanoelectromechanical system (NEMS), microelectromechanical system (MEMS), nanodevice, or chemical sensor is provided. may have been formed. The device may be an organic electronic device such as an organic light emitting diode and an organic solar cell. As such, in the present embodiment, the substrate 10 may be the bare substrate or the element formed on top of the bare substrate.

An etching target layer 20 may be formed on the substrate 10 . The layer to be etched 20 is a layer that is etched using the photoresist pattern as an etching mask to form a pattern after forming a photoresist pattern, and may be formed of various materials used in a semiconductor process. As an example, the layer to be etched 20 may be a metal film, a semiconductor film, an insulating film, or a composite film including any one of these. The metal film is for forming a wire, and may be aluminum, tungsten, titanium, or a composite film containing any one of these. The semiconductor film may be a silicon film, for example, a single crystal silicon film, polysilicon film, an amorphous silicon film, or a composite film including any one of these. The insulating film may include an inorganic insulating film such as a silicon oxide film or a silicon nitride film; organic insulating films such as amorphous carbon films; Or it may be a composite film containing any one of these. In one example, the layer to be etched 20 may be the bare substrate.

As an example of the surface functional group of the layer 20 to be etched, it may have a hydroxyl group, a thiol group, an amine group, or a phosphine group, or may be surface-treated to have it.

A multilayer molecular film photoresist 30 having a molecular beam structure may be formed on the layer 20 to be etched.

The multilayer molecular film photoresist 30 may include a plurality of molecular lines ML in a transverse direction to which inorganic single molecules M1 , M2 , or M3 are directly or indirectly connected by bonding. At this time, being indirectly connected means that an organic single molecule (O1, O2, or O3) or a functional group, which will be described later as an example of another single molecule, is bonded between the inorganic single molecules (M1, M2, or M3). can mean The bond may be a covalent bond or a coordinate bond. In one example, the molecular lines ML may each extend in an upward direction, for example, a vertical direction with respect to the substrate 10, and the transverse direction may be a direction substantially parallel to the surface of the substrate 10. .

In this embodiment, since the multilayer molecular film photoresist 30 is formed using atomic layer deposition or molecular layer deposition, almost all of the molecular lines in the multilayer molecular film photoresist 30 (ML) may have substantially the same laminated structure. As a result, the molecular lines ML in the multilayer molecular film photoresist 30 may have the same inorganic monolayer and the same organic monolayer in the lateral direction. In other words, the inorganic monomolecules included in the molecular lines are equally arranged in the lateral direction to form an inorganic monomolecular layer, and the organic monomolecules provided in the molecular lines are equally arranged in the lateral direction to form an organic monomolecular layer. .

The multilayer molecular film photoresist 30 may be an organic/inorganic multilayer molecular film photoresist. Specifically, in the multilayer molecular film photoresist 30, organic single molecules (O1, O2, O3) are interposed between some inorganic single molecules (M1, M2, M3) included in each molecular line (ML). can mean combined. In this case, the multilayer molecular film photoresist 30 has a plurality of molecular lines (ML) in which organic single molecules (O1, O2, and O3) and inorganic single molecules (M1, M2, and M3) are connected by bonds in the transverse direction. and may have van der Waals interactions (VI) between organic single molecules O1 , O2 , and O3 in adjacent molecular lines ML among the molecular lines ML. At this time, the van der Waals interaction (VI) may serve to stabilize the molecular lines (ML) adjacent in the lateral direction so that the pattern does not collapse even when the aspect ratio is high. In one example, the van der Waals interaction may be a π-π bond between aromatic groups.

The multilayer molecular film photoresist 30 may have a layer configuration represented by Chemical Formula 1 below.

[Formula 1]

In Chemical Formula 1, one of * may be a bond with a functional group in a lower layer or a functional group in a lower single molecule, and the other may be a bond with a functional group in an upper layer or a functional group in an upper single molecule. In this case, the bond may be, for example, a covalent bond. OM may be an organic monomer. Specifically, the OM may be an organic single molecule represented by Chemical Formula 3 below. In Formula 1, m may be 0 to 10, n may be 1 to 10, and l may be 1 to 10000, specifically 20 to 1000, and more specifically 25 to 100. Specifically, m may be 1 to 2, for example, m may be 1. n Also, 1 to 2, as an example, n may be 1.

MM may be an inorganic single molecule containing a metal element, specifically, an organometallic single molecule. MM is, for example, a light absorbing inorganic single molecule containing a metal element having a d orbital, a photoreactive inorganic single molecule including Zr, Al, Hf, Zn, or In, or Al, Ti, Cu, W, Or it may be an etch-resistant inorganic single molecule containing Zn. The metal element having the d orbital, specifically, the 4d or 5d orbital may be, for example, Sn, Sb, Te, or Bi. Here, the classification of inorganic single molecules refers to the main function, and all inorganic single molecules described can perform light absorption and photoreaction. The MM may be an organometallic single molecule represented by Formula 2 below, specifically Formula 2A, 2B, or 2B below.

[Formula 2]

In Formula 2, one of * may be a bond with a functional group in a lower layer or a functional group in a lower single molecule, and the other may be a bond with a functional group in an upper layer or a functional group in an upper single molecule. In this case, the bond may be, for example, a covalent bond. Z ₁ and Z ₂ are a bond regardless of each other, 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 linear or branched alkylene group or unsubstituted linear or branched alkyleneamino, C1 to C20 substituted or unsubstituted linear or branched alkylenesilylamino, C1 to C20 substituted or unsubstituted linear or branched alkylenethio, C1 to C20 It may be a substituted or unsubstituted linear or branched alkylene seleno, or a C1 to C20 substituted or unsubstituted linear or branched alkylene phosphino. M ⁰ 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 etch-resistant metal atom such as Al, Ti, Cu, W, or Zn. The metal element having the d orbital, specifically, the 4d or 5d orbital may be, for example, Sn, Sb, Te, or Bi. X _a can be O, S, Se, NR (R is H or CH ₃ ) or PR (R is H or CH ₃ ).

L _a and L _b are ligands bound to M ⁰ , and the sum of the number of these ligands, na and nb, can be determined by the coordination number caused by M ⁰ . For example, the sum of na and nb may be an integer from 1 to 4. L _a and L _b are, regardless of each other, a halogen group (ex. Cl, Br, or I), a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkyl group It may be an organic group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, or a C1 to C5 alkylphosphino group. Here, the C1 to C5 alkyl groups may be substituted or unsubstituted, linear or branched alkyl groups. In addition, when na and/or nb in Formula 2 is 2 or more, L _a and/or L _b may be selected regardless of each other among the above examples. In one example, when the sum of na and nb is 2 or more, two of L _a and L _b may be taken together with M ⁰ to which they are attached to form a heterocyclyl or heteroaryl. Each bond between Z ₁ , Z ₂ , L _a , or L _b and M ⁰ may be a covalent bond or a coordinate bond regardless of each other.

In one example, the multilayer molecular film photoresist 30 includes a light absorption layer (FL ₁ ), a photoreaction layer (FL ₂ ), and an etch-resistant layer ( FL ₃ ) may be provided with at least one layer. At this time, the classification of each layer refers to the main function, and all layers may generate secondary electrons according to light absorption and perform a photoreaction described later. As an example, the multilayer molecular film photoresist 30 may include at least a light absorption layer FL ₁ . The stacking order of the light absorption layer (FL ₁ ), the photoreaction layer (FL ₂ ), and the etching resistance layer (FL ₃ ) depends on the type of the layer to be etched 20 and/or the type of pattern to be formed through photolithography. may vary depending on

The light absorbing layer FL ₁ may be a layer capable of generating secondary electrons by absorbing radiation and having excellent radiation, specifically, EUV or E-beam absorption. The light absorption layer FL ₁ may have a layer structure represented by Chemical Formula 1A below.

[Formula 1A]

In Chemical Formula 1A, one of * may be a bond with a functional group in a lower layer or a functional group in a lower single molecule, and the other may be a bond with a functional group in an upper layer or a functional group in an upper single molecule. In this case, the bond may be, for example, a covalent bond. M1 is a light-absorbing inorganic single molecule, for example, a metal element having a d orbital, specifically a 4d or 5d orbital, and may be an organometallic single molecule including Sn, Sb, Te, or Bi, as an example, and O1 may be an organic single molecule. Also, 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 Also, 1 to 2, for example, n1 may be 1.

The light-absorbing inorganic single molecule (M1) may be a light-absorbing organometallic single molecule represented by Formula 2A, and when n1 is 2 or more or l1 is 2 or more in Formula 1A, the light-absorbing inorganic single molecule (M1 of each layer) ) may be the same as or different from each other.

[Formula 2A]

In Formula 2A, one of * may be a bond with a functional group in a lower layer or a functional group in a lower single molecule, and the other may be a bond with a functional group in an upper layer or a functional group in an upper single molecule. In this case, the bond may be, for example, a covalent bond. Z ₁ and Z ₂ are a bond regardless of each other, 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 linear or branched alkylene group or unsubstituted linear or branched alkyleneamino, C1 to C20 substituted or unsubstituted linear or branched alkylenesilylamino, C1 to C20 substituted or unsubstituted linear or branched alkylenethio, C1 to C20 It may be a substituted or unsubstituted linear or branched alkylene seleno, or a C1 to C20 substituted or unsubstituted linear or branched alkylene phosphino. M ^a is an inorganic atom having excellent radiation, specifically EUV or E-beam absorption, and may be a metal atom having a d orbital, for example, a 4d or 5d orbital. Specifically, the metal atom may be Sn, Bi, Sb, or Te. X _a can be O, S, Se, NR (R is H or CH ₃ ) or PR (R is H or CH ₃ ).

In Chemical Formula 2A, L ₁ and L ₂ are ligands bound to M ^a , and the sum of n1 and n2 , which are the number of ligands, may be determined by the coordination number caused by M ^a . For example, the sum of n1 and n2 may be an integer from 1 to 4. L ₁ and L ₂ are independently of each other a halogen group (ex. Cl, Br, or I), a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkyl group It may be an alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, or a C1 to C5 alkylphosphino group. Here, the C1 to C5 alkyl groups may be substituted or unsubstituted, linear or branched alkyl groups. In addition, when n1 and/or n2 is 2 or more in Formula 2A, L ₁ and/or L ₂ may be selected regardless of each other among the above examples. In one example, when the sum of n1 and n2 is greater than or equal to 2, two of L ₁ and L ₂ may be taken together with M ^a to which they are attached to form a heterocyclyl or heteroaryl. Each bond between Z ₁ , Z ₂ , L ₁ , or L ₂ and M ^a may be a covalent bond or a coordinate bond regardless of each other.

The organic single molecule (O1) may be represented by the following Chemical Formula 3, and when m1 is 2 or more or l1 is 2 or more in Chemical Formula 1A, the organic single molecules (O1) of each layer may be the same as or different from each other.

[Formula 3]

In Chemical Formula 3, one of * may be a bond with a functional group in a lower layer or a functional group in a lower single molecule, and the other may be a bond with a functional group in an upper layer or a functional group in an upper single molecule. In this case, the bond may be, for example, a covalent bond. X _b can be O, S, Se, NR (R is H or CH ₃ ) or PR (R is H or CH ₃ ).

In one example, MR of Chemical Formula 3 may be a substituted or unsubstituted aromatic ring. Here, the substitution may be one in which hydrogen of an aromatic ring is substituted with various functional groups. When MR is an aromatic ring, Z ₃ and Z ₄ may each independently be a bond or a C1 to C5 substituted or unsubstituted, linear or branched alkylene group. Here, the substitution may be one in which the hydrogen of the alkylene group is substituted with OH, SH, SeH, NR ₂ (R is H or CH ₃ regardless of each other) or PR ₂ (R is H or CH ₃ regardless of each other) .

In another example, MR in Formula 3 may be a C1 to C18 substituted or unsubstituted linear or branched alkylene group. Substitution is a functional group in which hydrogen of an alkylene group can be crosslinked by radiation, for example, substitution by a functional group including a vinyl group. or OH, SH, SeH, NR ₂ (R is H or CH ₃ regardless of each other) or PR ₂ (R is H or CH ₃ regardless of each other). When MR is an alkylene group, Z ₃ and Z ₄ may be bonds.

The multilayer molecular film photoresist 30 may further include a photoreactive layer FL ₂ in addition to the light absorption layer FL ₁ . The photoreactive layer FL ₂ may have a layer structure represented by Chemical Formula 1B below.

[Formula 1B]

In Chemical Formula 1B, one of * may be a bond with a functional group in a lower layer or a functional group in a lower single molecule, and the other may be a bond with a functional group in an upper layer or a functional group in an upper single molecule. Here, the bond may be, for example, a covalent bond. M2 is a photoreactive inorganic single molecule, and may be, for example, an organometallic single molecule including Zr, Al, Hf, Zn, or In, and O2 may be an organic single molecule. Also, 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 Also, 1 to 2, for example, n2 may be 1.

The photoreactive inorganic single molecule (M2) may be a photoreactive organometallic single molecule represented by Formula 2B, and when n2 is 2 or more or l2 is 2 or more in Formula 2B, the photoreactive inorganic single molecule (M2) of each layer ) may be the same as or different from each other.

[Formula 2B]

In Chemical Formula 2B, one of * may be a bond with a functional group in a lower layer or a functional group in a lower single molecule, and the other may be a bond with a functional group in an upper layer or a functional group in an upper single molecule. Here, the bond may be, for example, a covalent bond. Z ₁ and Z ₂ are a bond regardless of each other, 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 linear or branched alkylene group or unsubstituted linear or branched alkyleneamino, C1 to C20 substituted or unsubstituted linear or branched alkylenesilylamino, C1 to C20 substituted or unsubstituted linear or branched alkylenethio, C1 to C20 It may be a substituted or unsubstituted linear or branched alkylene seleno, or a C1 to 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 _a can be O, S, Se, NR (R is H or CH ₃ ) or PR (R is H or CH ₃ ).

L ₃ and L ₄ are ligands bound to M ^b , and the sum of n1 and n2 , the number of these ligands, can be determined by the coordination number caused by M ^b . For example, the sum of n1 and n2 may be an integer from 1 to 4. L ₃ and L ₄ are independently of each other a halogen group (ex. Cl, Br, or I), a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkyl group It may be an organic group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, or a C1 to C5 alkylphosphino group. Here, the C1 to C5 alkyl groups may be substituted or unsubstituted, linear or branched alkyl groups. In addition, when n1 and/or n2 is 2 or more in Formula 2B, L ₃ and/or L ₄ may be selected regardless of each other among the above examples. In one example, when the sum of n1 and n2 is greater than or equal to 2, two of L ₃ and L ₄ may be taken together with the M ^b to which they are attached to form a heterocyclyl or heteroaryl. Each bond between Z ₁ , Z ₂ , L ₃ , or L ₄ and M ^b may be a covalent bond or a coordinate bond regardless of each other.

The organic single molecule (O2) may be represented by Chemical Formula 3 above. However, it may be the same as or different from the organic single molecule (O1) in the light absorption layer (FL ₁ ), and when m2 is 2 or more or l2 is 2 or more in Chemical Formula 1B, the organic single molecule (O2) of each layer is the same as each other. or may be different.

By secondary electrons generated in the light absorption layer (FL ₁ ) or by secondary electrons generated from a metal included in the photoreactive inorganic single molecule (M2) and/or the etched inorganic single molecule (M3) described below, adjacent A crosslink may be formed between the photoreactive inorganic single molecules M2 in the molecular beams ML. Specifically, M ^b -L ₄ and L ₃ -M ^b bonds between adjacent photoreactive inorganic monomers (M2) react with the secondary electrons to form M ^b -Y ₂ -M ^b bonds. can do. This M ^b -Y ₂ -M ^b bond is an example of a developer that develops a multilayer molecular film photoresist pattern formed by exposure, and may not be etched by a developing gas or a developing plasma. To this end, the type of M ^b may be selected as above. Here, Y ₂ may be O, S, Se, N, or P.

However, the present invention is not limited thereto, and crosslinks may also be formed between light absorbing inorganic single molecules M1 in adjacent molecular lines ML by secondary electrons generated in the light absorbing layer FL ₁ . Specifically, the M ^a -L ₂ and L ₁ -M ^a bonds between the adjacent light-absorbing inorganic monomers M1 react with the secondary electrons to form a M ^a -Y ₁ -M ^a bond. can do. This bond may also not be etched by the developer. Here, Y ₁ may be O, S, Se, N, or P.

The multilayer molecular film photoresist 30 may further include an etching resistant layer FL ₃ in addition to the light absorption layer FL ₁ . The etching resistant layer FL ₃ may have a layer structure represented by Chemical Formula 1C below.

[Formula 1C]

In Chemical Formula 1C, one of * may be a bond with a functional group in a lower layer or a functional group in a lower single molecule, and the other may be a bond with a functional group in an upper layer or a functional group in an upper single molecule. Here, the bond may be, for example, a covalent bond. M3 is an etch-resistant inorganic single molecule, and may be, for example, an organometallic single molecule including Al, Ti, Cu, W, or Zn, and O3 may be an organic single molecule. Also, 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. n3 Also, 1 to 2, as an example, n3 may be 1.

The etch-resistant inorganic single molecule (M3) may be an etch-resistant organometallic single molecule represented by Formula 2C, and when n3 is 2 or more or l3 is 2 or more in Formula 1C, the etch-resistant inorganic single molecule (M3 ) may be the same as or different from each other.

[Formula 2C]

In Chemical Formula 2C, one of * may be a bond with a functional group in a lower layer or a functional group in a lower single molecule, and the other may be a bond with a functional group in an upper layer or a functional group in an upper single molecule. Here, the bond may be, for example, a covalent bond. Z ₁ and Z ₂ are a bond regardless of each other, 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 linear or branched alkylene group or unsubstituted linear or branched alkyleneamino, C1 to C20 substituted or unsubstituted linear or branched alkylenesilylamino, C1 to C20 substituted or unsubstituted linear or branched alkylenethio, C1 to C20 It may be a substituted or unsubstituted linear or branched alkylene seleno, or a C1 to 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 _a can be O, S, Se, NR (R is H or CH ₃ ) or PR (R is H or CH ₃ ).

L ₅ and L ₆ are ligands bound to M ^c , and the sum of n1 and n2 , the number of these ligands, can be determined by the coordination number caused by M ^c . For example, the sum of n1 and n2 may be an integer from 1 to 4. L ₅ and L ₆ are independently of each other a halogen group (ex. Cl, Br, or I), a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkyl group It may be an organic group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, or a C1 to C5 alkylphosphino group. Here, the C1 to C5 alkyl groups may be substituted or unsubstituted, linear or branched alkyl groups. In addition, when n1 and/or n2 is 2 or more in Formula 2C, L ₅ and/or L ₆ may be selected regardless of each other among the above examples. In one example, when the sum of n1 and n2 is greater than or equal to 2, two of L ₅ and L ₆ may be taken together with the M ^c to which they are attached to form a heterocyclyl or heteroaryl. Each bond between Z ₁ , Z ₂ , L ₅ , or L ₆ and M ^c may be a covalent bond or a coordinate bond regardless of each other.

The organic single molecule (O3) may be represented by Chemical Formula 3 above. The organic single molecule (O3) may be the same as or different from the organic single molecule (O3) in the light absorption layer (FL ₁ ) or the organic single molecule (O2) in the photoreactive layer (FL ₂ ). When m3 is 2 or more or l3 is 2 or more, organic monomers (O3) in each layer may be the same or different.

By secondary electrons generated in the light absorption layer (FL ₁ ) or by secondary electrons generated from a metal included in the photoreactive inorganic single molecule (M2) and/or the etch-resistant inorganic single molecule (M3), adjacent Crosslinks may be formed between the etch-resistant inorganic single molecules M3 in the molecular wires ML. Specifically, M ^c -L ₅ or M ^c -L ₆ bonds in the etch-resistant inorganic monomolecules (M3) adjacent to each other react with the secondary electron to form an M ^c -Y ₃ -M ^c bond. can do. This M ^c -Y ₃ -M ^c bond may not be etched by a developer and, as an example of an etchant for etching the layer 20 to be etched, may not be etched even by plasma. To this end, the type of M ^c can be selected as above. Here, Y ₃ may be O, S, Se, N, or P.

In the light absorption layer FL ₁ shown in FIG. 2 , m1 in FIG. 1 is 1, n1 is 1, and l1 is 2. Although the light absorption layer FL ₁ is shown as an example in FIG. 2 , the photoreactive layer FL ₂ and/or the etching resistant layer FL ₃ of FIG. 1 may also have one of these exemplary structures.

As such, when m, m1, m2, m3 and n, n1, n2, n3 are all 1 in Formulas 1, 1A, 1B, or 1C, the multilayer molecular film photoresist 30 is an inorganic single molecule ( MM, M1, M2, or M3) and organic monomolecules (OM, O1, O2, or O3) may have a structure in which they are alternately stacked, and in this case, between the inorganic monomolecules (MM, M1, M2, or M3) As an organic single molecule (OM, O1, O2, or O3) is disposed in each, both an inorganic single molecule (MM, M1, M2, or M3) and an organic single molecule (OM, O1, O2, or O3) are placed on the bottom (single molecule). ) layer can be self-assembled. As a result, the molecular lines ML may each extend in a vertical direction, for example, in an upward direction with respect to the substrate 10 while being spaced apart from each other.

3 to 7 are schematic diagrams sequentially showing a photolithography method according to an embodiment of the present invention. 3 to 7 illustrate a case in which n1, n2, n3, m1, m2, m3, l1, l2, and l3 in FIG. 1 are all 1 in the multilayer molecular film photoresist 30 for convenience of description. In Formulas 2A, 2B, and 2C representing inorganic monomolecules (M1, M2, and M3), Z1 and Z2 are both bonds, and n1 and n2 are both 1.

Referring to FIG. 3 , a substrate 10 on which an etched layer 20 is formed 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 20 to be etched. The multilayer molecular film photoresist 30 may be the same as the embodiment described with reference to FIG. 1 except for the description below. In one embodiment, the multilayer molecular film photoresist 30 is described by taking an example in which an etch-resistant layer (FL ₃ ), a light absorption layer (FL ₁ ), and a photoreactive layer (FL ₂ ) are sequentially stacked. It is not limited, and the stacking order may vary depending on the type of the layer to be etched 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.

As an example, a light absorption layer FL ₁ may be formed on the layer 20 to be etched. Forming the light absorption layer FL ₁ may be performed using an atomic layer deposition method, specifically, a molecular layer deposition method.

In one example, the light absorbing layer FL ₁ is formed by performing a cycle including forming the light absorbing metal monomolecular layer M1 and forming the organic molecular layer O1 a plurality of times (l1 in Chemical Formula 1A). It can be. an organic precursor dosing step of dosing the organic precursor in the step of forming the organic molecular layer O1 and chemically bonding the organic precursor to the lower layer in a self-assembly manner; and a purge step of purging unreacted organic precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon.

The organic precursor may be represented by Formula 4 below.

[Formula 4]

In Formula 4, R _a1 and R _a2 may be hydrogen or an alkyl group of C1 to C2 independently of each other, and X _b and X _a are O, S, Se, NR regardless of each other (R is H or CH ₃ ) or PR (R is H or CH ₃ ). Meanwhile, Z ₃ , Z ₄ , and MR are as defined in Formula 3 above.

Specific examples of the organic precursor may be as follows.

In the step of dosing the organic precursor, a reaction according to Scheme 1 below may occur.

[Scheme 1]

In Scheme 1, R ₀ is a functional group on the surface of the lower layer, R ₀ is hydrogen, a hydroxy group, a thiol group, an amine group, a phosphine group, a C1 to C5 alkyl group, a C1 to C5 alkoxy group, a C1 to C5 alkoxy group, It may be a C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamine group, or a C1 to C5 alkylphosphino group. R _a1 X _b -Z ₃ -MR-Z ₄ -X _a R _a2 is an organic precursor, and each functional group is as defined in Chemical Formula 4 above.

Referring to Scheme 1, the organic precursor may self-assemble on the lower layer by reacting with functional groups on the surface of the lower layer. In this process, R ₀ R _a1 may be generated as a reaction by-product. Thereafter, in the purging step, the remaining organic precursor and the reaction byproducts may be purged.

A metal precursor dosing step of dosing a metal precursor in the step of forming the light absorbing metal monomolecular layer M1 and chemically bonding the metal precursor to the lower layer in a self-assembly manner; and a purge step of purging unreacted metal precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon.

A metal precursor for forming the light-absorbing metal monomolecular layer M1 may be represented by Chemical Formula 5A below.

[Formula 5A]

In Formula 5A, R _b1 and R _b2 are independently of each other a halogen group (ex. Cl, Br, or I), a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkoxy group, and a C1 to C5 alkylsilylamino group. It may be a C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, or a C1 to C5 alkylphosphino group. Here, the C1 to C5 alkyl groups may be substituted or unsubstituted linear or branched alkyl groups. Z ₁ , Z ₂ , L ₁ , L ₂ , n ₁ , n ₂ , and M ^a are as defined in Formula 2A. In addition, optionally two of R _bi , R _b2 , L ₁ , and L ₂ may be taken together with M ^a to which they are directly or indirectly bonded to form a heterocyclyl or heteroaryl. Alternatively, at least one of R _b1 and R _b2 may be in a state coordinated with M ^a .

Specific examples of the metal precursor for forming the light-absorbing metal monomolecular layer M1 may be as follows.

In the metal precursor, R1, R2, R3, and R4 are C1 to C5 regardless of each other.

It may be an alkyl group.

In the metal precursor dosing step, a reaction according to Reaction Formula 2 may occur.

[Scheme 2]

In Scheme 2, *-X _a R _a2 is a surface functional group of the lower layer, specifically, a surface functional group of the previously formed organic molecular layer (O1), and the metal precursor of Chemical Formula 5A is the surface of the previously formed organic molecular layer (O1). It may react with functional groups 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. Thereafter, in the purging step, the remaining metal precursor and the reaction byproducts may be purged. In Scheme 2, each functional group may be the same as defined in Chemical Formulas 4 and 5A.

Unlike the drawing, when the light absorption layer FL ₁ is formed of a plurality of metal monolayers M1 (when n1 in Formula 1A is 2 or more), a metal precursor dosing step and a purge step according to Scheme 2 described above are performed. Then, a reaction gas dosing step of dosing the reaction gas to react with the metal precursor chemically bonded to the lower layer; and a purge step of purging the unreacted reaction gas and the reaction product by supplying the purge gas to repeat the unit cycle. At this time, the reaction gas may be a gas containing hydrogen, oxygen (ex. O ₂ , O ₃ , H ₂ O), a gas containing nitrogen (ex. NH ₃ ), and the like.

A photoreactive layer FL _{2 may be formed on the light absorbing layer FL 1} or on the substrate before forming _{the light absorbing layer FL 1} _. Forming the photoreactive layer FL ₂ may be performed using an atomic layer deposition method, specifically, a molecular layer deposition method.

As an example, the photoreactive layer FL ₂ may be formed by performing a cycle including forming the photoreactive metal monomolecular layer M2 and forming the organic molecular layer O2 . The forming of the organic molecular layer O2 may be formed using the same or similar method as the method of forming the organic molecular layer O1 described in the light absorption layer FL ₁ . However, in the organic precursor dosing step of Reaction Scheme 1, -R ₀ may be substituted with -R _b2 which is an end group of the metal precursor self-assembled on the lower layer described in Scheme 2 above.

Forming the photoreactive metal monolayer M2 may include a metal precursor dosing step of dosing a metal precursor and chemically bonding the metal precursor to the lower layer in a self-assembly manner; and a purge step of purging unreacted metal precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon.

A metal precursor for forming the photoreactive metal monolayer M2 may be represented by Chemical Formula 5B below.

[Formula 5B]

In Formula 5B, R _b1 and R _b2 are independently of each other a halogen group (ex. Cl, Br, or I), a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy, C1 to C5 It may be a C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, or a C1 to C5 alkylphosphino group. Here, the C1 to C5 alkyl groups may be substituted or unsubstituted, linear or branched alkyl groups. Z ₁ , Z ₂ , L ₃ , L ₄ , n ₁ , n ₂ , and M ^b are as defined in Formula 2B. In addition, optionally two of R _bi , R _b2 , L ₃ , and L ₄ may be taken together with M ^b to which they are directly or indirectly bonded to form a heterocyclyl or heteroaryl. Alternatively, at least one of R _b1 and R _b2 may be in a state coordinated with M ^b .

Specific examples of the metal precursor for forming the photoreactive metal monolayer M2 may be as follows.

In the metal precursor dosing step, a reaction according to Reaction Formula 3 may occur.

[Scheme 3]

In Reaction Formula 3, *-X _a R _a2 is a surface functional group of the lower layer, specifically, a surface functional group of the organic molecular layer (O2) formed previously, and the metal precursor of Formula 5B is the surface of the organic molecular layer (O2) formed previously. It may react with functional groups 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. Thereafter, in the purging step, the remaining metal precursor and the reaction byproducts may be purged. In Scheme 3, each functional group may be the same as defined in Formula 4 and Formula 5B.

Unlike the drawing, when the photoreaction layer FL ₁ is formed of a plurality of metal monomolecular layers M2 (when n2 in Formula 1B is 2 or more), a metal precursor dosing step and a purge step according to Scheme 3 described above After performing, a reaction gas dosing step of dosing a reaction gas to react with a metal precursor chemically bonded to the lower layer; and a purge step of purging the unreacted reaction gas and the reaction product by supplying the purge gas to repeat the unit cycle. At this time, the reaction gas may be hydrogen, a gas containing oxygen (ex. O ₂ , O ₃ , H ₂ O), a gas containing nitrogen (ex. NH ₃ ), and the like.

An etching resistant layer FL ₃ may be formed on the light absorbing layer FL ₁ or on the substrate before forming the light absorbing layer FL ₁ . Forming the etching resistant layer FL ₃ may be performed using an atomic layer deposition method, specifically, a molecular layer deposition method.

As an example, the etch-resistant layer FL ₃ may be formed by performing a cycle including forming the etch-resistant metal monomolecular layer M3 and forming the organic molecular layer O3 . The forming of 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 in the light absorption layer FL ₁ . However, in the organic precursor dosing step of Scheme 1, -R ₀ may be a surface functional group bonded to the surface to be etched.

Forming the etching-resistant metal monolayer M3 may include a metal precursor dosing step of dosing a metal precursor and chemically bonding the metal precursor to the lower layer in a self-assembly manner; and a purge step of purging unreacted metal precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon.

A metal precursor for forming the etching-resistant metal monolayer M3 may be represented by Chemical Formula 5C.

[Formula 5C]

In Formula 5C, R _b1 and R _b2 are independently of each other a halogen group (ex. Cl, Br, or I), a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkoxy group, and a C1 to C5 alkylsilylamino group. It may be a C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, or a C1 to C5 alkylphosphino group. Here, the C1 to C5 alkyl groups may be substituted or unsubstituted, linear or branched alkyl groups. Z ₁ , Z ₂ , L ₅ , L ₆ , n ₁ , n ₂ , and M ^c are as defined in Formula 2C. In addition, optionally two of R _bi , R _b2 , L ₅ , and L ₆ may be taken together with M ^c to which they are directly or indirectly bonded to form a heterocyclyl or heteroaryl. Alternatively, at least one of _Rb1 and _Rb2 may be coordinately bonded to M ^c .

Specific examples of the metal precursor for forming the etch-resistant metal monolayer M3 may be as follows.

In the metal precursor dosing step, a reaction according to Reaction Formula 4 may occur.

[Scheme 4]

In Reaction Formula 4, -X _a R _a2 is a surface functional group of the lower layer, specifically, a surface functional group of the organic molecular layer (O3) formed previously, and the metal precursor of Formula 5C is a surface functional group of the organic molecular layer (O3) formed previously. and may be self-assembled on the surface of the organic molecular layer O3. In this process, R _a2 R _b1 may be produced as a reaction by-product. Thereafter, in the purging step, the remaining metal precursor and the reaction byproducts may be purged. In Scheme 4, each functional group may be the same as defined in Formula 4 and Formula 5C.

Unlike the drawing, when the etching-resistant layer FL ₁ is formed of a plurality of metal monolayers M3 (when n3 in Formula 1C is 2 or more), a metal precursor dosing step and a purge step according to Scheme 4 described above After performing, a reaction gas dosing step of dosing a reaction gas to react with a metal precursor chemically bonded to the lower layer; and a purge step of purging the unreacted reaction gas and the reaction product by supplying the purge gas to repeat the unit cycle. At this time, the reaction gas may be hydrogen, a gas containing oxygen (ex. O ₂ , O ₃ , H ₂ O), a gas containing nitrogen (ex. NH ₃ ), and the like.

However, without being limited to the above, in another embodiment of the present invention, the multilayer molecular film photoresist 30 is formed by forming a metal monomolecular layer (MM in Formula 1) and forming an organic molecular layer (OM in Formula 1). It can be formed by performing a cycle comprising the steps. The forming of the organic molecular layer (OM of Chemical Formula 1) may include an organic precursor dosing step of dosing the organic precursor of Chemical Formula 4 to chemically bond the organic precursor to the lower layer in a self-assembly manner; and a purge step of purging unreacted organic precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon. In the step of dosing the organic precursor, a reaction according to Scheme 1 may occur.

Forming the metal monomolecular layer (MM of Chemical Formula 1) may include a metal precursor dosing step of dosing a metal precursor of Chemical Formula 5 to chemically bond the metal precursor to a lower layer in a self-assembly manner; and a purge step of purging unreacted metal precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon.

[Formula 5]

In Formula 5, R _b1 and R _b2 are independently of each other a halogen group (ex. Cl, Br, or I), a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkoxy group, and a C1 to C5 alkylsilylamino group. It may be a C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, or a C1 to C5 alkylphosphino group. Here, the C1 to C5 alkyl groups may be substituted or unsubstituted linear or branched alkyl groups. Z ₁ , Z ₂ , L _a , L _b , n _a , n _b , and M ⁰ are as defined in Formula 2. In addition, optionally two of R _bi , R _b2 , L _a , and L _b may be taken together with M ⁰ to which they are directly or indirectly bonded to form a heterocyclyl or heteroaryl. Alternatively, at least one of R _b1 and R _b2 may be in a state coordinated with M ⁰ .

In the metal precursor dosing step, a reaction according to Reaction Formula 5 may occur.

[Scheme 5]

In Reaction Formula 5, *-X _a R _a2 is a surface functional group of the lower layer, specifically, a surface functional group of the previously formed organic molecular layer (O), and the metal precursor of Chemical Formula 5 is the surface of the previously formed organic molecular layer (O). It may react with functional groups 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. Thereafter, in the purging step, the remaining metal precursor and the reaction byproducts may be purged. In Reaction Scheme 5, each functional group may be the same as defined in Chemical Formulas 4 and 5.

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

Referring to FIG. 4 , a portion of the multilayer molecular film photoresist 30 may be irradiated with radiation (hv), specifically, EUV or Ebeam. In this case, as an example of a d orbital in the light absorption layer FL ₁ , M ^a , which is a metal atom having a 4d or 5d orbital, may absorb the radiation to generate secondary electrons. However, it is not limited thereto, and metal atoms or other elements in the photoreactive layer FL ₂ and/or the etching resistant layer FL ₃ may also absorb radiation to generate secondary electrons.

Crosslinks may be formed between photoreactive inorganic single molecules M2 in adjacent molecular lines ML by secondary electrons generated in the light absorption layer FL ₁ . Specifically, M ^b -L ₄ and L ₃ -M ^b in the photoreactive inorganic single molecules (M2) adjacent to each other react by the secondary electron to form an M ^b -Y ₂ -M ^b bond. can Here, Y ₂ may be O, S, Se, N, or P. In addition, cross-links may also be formed between light-absorbing inorganic single molecules M1 in adjacent molecular lines ML by secondary electrons generated in the light-absorbing layer FL ₁ . Specifically, M ^a -L ₂ and L ₁ -M ^a bonds in the light absorbing inorganic monomers M1 may react with the secondary electrons to form M ^a -Y ₁ -M ^a bonds. . Here, Y ₁ may be O, S, Se, N, or P. Also, crosslinks may be formed between etch-resistant inorganic single molecules M3 in adjacent molecular lines ML by secondary electrons generated in the light absorption layer FL ₁ . Specifically, the M ^c -L ₆ and L ₅ -M ^c bonds in the etched inorganic monomers (M3) may react with the secondary electron to form an M ^c -Y ₃ -M ^c bond. . Here, Y ₃ may be O, S, Se, N, or P.

Referring to FIG. 5 , the multilayer molecular film photoresist 30 exposed by radiation may be exposed to a developer. In this case, the multilayer molecular film photoresist pattern 31 is formed by removing the cross-linked portion between the inorganic monomolecules M1, M2, and M3 in the adjacent molecular lines ML by removing the crosslinks by the developer. can be formed The developer is a developing solution, for example, water, isopropyl alcohol (IPA), methyl isobutyl ketone (MIBK), tetramethylammonium hydroxide (TMAH), or a developing gas, for example, CF ₄ , Ar, O ₂ , CHF ₃ etc. or a plasma generated therefrom.

Referring to FIG. 6 , the film to be etched 20 may be etched using the multilayer molecular film photoresist pattern 31 as a mask. This etching may be, for example, plasma etching. At this time, the etching resistance of the multilayer molecular film photoresist pattern 31 is increased due to the M ^c -Y ₃ -M ^c bond between the etch-resistant inorganic single molecules M3, thereby selectively forming the film to be etched 20. can be etched with

Referring to FIG. 7 , the multilayer molecular film photoresist pattern 31 may be removed. This can be done using the ashing method.

Referring again to FIG. 3, a molecular layer deposition equipment for manufacturing a multilayer molecular film photoresist will be described. Except for the description below, reference will be made to what has been described with reference to FIGS. 1, 2a, 2b, and 3 .

Molecular layer deposition equipment according to an embodiment of the present invention is a cycle including the step of forming a metal monomolecular layer (MM of Formula 1) and the step of forming an organic molecular layer (OM of Formula 1) a plurality of times, specifically Formula 1 It can be performed as many times as indicated by l of The forming of the organic molecular layer (OM of Chemical Formula 1) may include an organic precursor dosing step of dosing the organic precursor of Chemical Formula 4 to chemically bond the organic precursor to the lower layer in a self-assembly manner; and a purge step of purging unreacted organic precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon. In the step of dosing the organic precursor, a reaction according to Scheme 1 may occur.

The forming of the metal monolayer (MM of Chemical Formula 1) may include a metal precursor dosing step of dosing the metal precursor of Chemical Formula 5 to chemically bond the metal precursor to the lower layer in a self-assembly manner; and a purge step of purging unreacted metal precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon. In the metal precursor dosing step, a reaction according to Scheme 5 may occur. Specifically, the metal precursor may be represented by Chemical Formulas 5A, 5B, or 5C. In addition, specifically, the reaction according to Reaction Formula 2, 3, or 4 may occur in the metal precursor dosing step.

In the molecular layer deposition equipment according to an embodiment of the present invention, a cycle including forming a light absorbing metal monomolecular layer (M1) and forming an organic molecular layer (O1) on a substrate is specifically specified a plurality of times. The light absorbing layer FL 1 may be formed by performing the light absorption layer FL ₁ as many times as indicated by l1 in Chemical Formula 1A.

an organic precursor dosing step of dosing the organic precursor of Chemical Formula 4 in the forming of the organic molecular layer O1 and chemically bonding the organic precursor to a lower layer in a self-assembly manner; and a purge step of purging unreacted organic precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon. In the step of dosing the organic precursor, a reaction according to Scheme 1 may occur.

The forming of the light-absorbing metal monolayer M1 may include a metal precursor dosing step of dosing the metal precursor of Chemical Formula 5A to chemically bond the metal precursor to the lower layer in a self-assembly manner; and a purge step of purging unreacted metal precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon. In the metal precursor dosing step, a reaction according to Scheme 2 may occur.

Forming a photoreactive metal monomolecular layer (M2) on the light absorbing layer (FL ₁ ) or on the substrate before forming the light absorbing layer (FL ₁ ) and forming an organic molecular layer (O2). The photoreactive layer FL ₂ may be formed by performing the cycle a plurality of times, specifically, as many times as indicated by l2 in Chemical Formula 1B. The forming of the organic molecular layer O2 may be formed using the same or similar method as the method described for the light absorption layer FL ₁ .

Forming the photoreactive metal monolayer M2 may include a metal precursor dosing step of dosing the metal precursor of Chemical Formula 5B to chemically bond the metal precursor to the lower layer in a self-assembly manner; and a purge step of purging unreacted metal precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon. In the metal precursor dosing step, a reaction according to Scheme 3 may occur.

Forming an etching-resistant metal monomolecular layer (M3) on the light absorption layer (FL ₁ ) or on the substrate before forming the light absorption layer (FL ₁ ) and forming an organic molecular layer (O3). The etching resistant layer FL ₃ may be formed by performing the cycle a plurality of times, specifically, as many times as indicated by l3 in Chemical Formula 1C. The forming of the organic molecular layer O3 may be formed using the same or similar method as the method described for the light absorption layer FL ₁ .

Forming the etching-resistant metal monolayer M3 may include a metal precursor dosing step of dosing the metal precursor of Chemical Formula 5C to chemically bond the metal precursor to the lower layer in a self-assembly manner; and a purge step of purging unreacted metal precursors and reaction products by supplying a purge gas. Here, the purge gas may be argon. In the metal precursor dosing step, a reaction according to Scheme 4 may occur.

As described above, in the multilayer molecular film photoresist 30 according to an embodiment of the present invention, inorganic single molecules and organic single molecules connected by bonding in the molecular lines are formed by self-assembly, so that each molecular line is formed on the top of the substrate. direction, and the molecular lines may be uniformly arranged in the transverse direction.

At this time, the distance between the molecular lines (D in FIG. 1 or 4) is very small, such as 1 nm or less, specifically 0.5 nm or less. In addition, as the separation between molecular lines rather than particles during exposure and development, Line Edge Roughness (LER), which means pattern side roughness, can be very low as 1.2 nm or less, and resolution is also 6 nm The following can be greatly improved. In addition, the multilayer molecular film photoresist 30 includes a light-absorbing inorganic single molecule (M1) having an inorganic atom having a very high light absorption rate for EUV, specifically, a metal atom having a 4d or 5d orbital, Even for EUV with low stochastic failure, high photosensitivity (ex. 10 mJ/cm ² ) can be exhibited.

Hereinafter, preferred experimental examples are presented to aid understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited by the following experimental examples.

8 shows a unit cycle configuration for forming an inorganic molecular layer.

Referring to FIG. 8, a unit cycle of dosing DEZ (diethylzinc) in the chamber for 2 seconds, purging the chamber for 30 seconds, dosing water (H ₂ O) for 2 seconds, and purging the chamber for 30 seconds A plurality of times (30 times) was performed to form a ZnO inorganic molecular layer.

Figure 9 is a vertical design formed with reference to Figure 8 This is a SEM image taken after patterning the inorganic multilayer molecular film photoresist. Specifically, after irradiating e ^- beam at a voltage of 100 kV and a dose of 2500 uC/cm ² on the vertically designed inorganic multilayer molecular film formed with reference to FIG. 8, in TMAH (Tetramethylammonium hydroxide) in H ₂ O It was developed by sonication for 2 minutes.

Referring to FIG. 9 , it can be seen that a pattern having a line width of 1 μm and a pattern having a line width of 500 nm are clearly formed.

Referring to FIG. 10, a substrate is loaded into a chamber, and while the substrate temperature is maintained at 100 to 300° C. (specifically, 100 to 150° C.), Hf precursor (Tetrakisdimethylamido Hafnium) and Ti precursor (Tetrakisdimethylamido Titanium) are used as inorganic precursors. , Al precursor (Trimethyl Aluminum), or DEZ (diethylzinc) at a pressure of 0.01 to 10 torr (0.05 to 0.5 torr), dosing for 1 second, purging the chamber for 5 seconds, and 4-mercaptophenol as an organic precursor at a pressure of 0.01 to 10 torr (0.01 to 0.5 torr). Dosing at a pressure of 10 torr (0.01 torr) for 1 second and purging the chamber for 5 seconds were performed multiple times (about 30 times) to form a multilayer molecular film photoresist having a thickness of about 20 nm.

11A, 11B, and 11C are SEM images taken after patterning the photoresist formed using the method described with reference to FIG. 10 . Specifically, after exposure by irradiating e ^- beam on the photoresist formed with reference to FIG. 10 under conditions of a voltage of 100 kV, a voltage of 100 pA, and a dose of 2500 uC/cm ² , TMAH (Tetramethylammonium hydroxide) in H ₂ O It was developed by sonicating for 2 minutes in

Referring to FIGS. 11A, 11B, and 11C , it can be seen that a pattern having a half pitch and a line width of 500 nm is clearly formed. At this time, a pattern is formed in the exposed portion, and the photoresist according to the present embodiment may be defined as a negative photoresist.

FIG. 12 is a graph showing the electron beam sensitivity of a photoresist formed using the method described with reference to FIG. 10 . Specifically, after exposure by irradiating e-beam on the photoresist formed with reference to FIG. 10 under conditions of a voltage of 100 kV, 100 pA and a dose of 1 to 10,000 uC/cm ² , TMAH (Tetramethylammonium hydroxide) in H It was developed by ultrasonic treatment for 2 minutes in ₂ O, and the thickness of the pattern according to the amount of exposure was measured and expressed.

Referring to FIG. 12, in this experiment, the normalized thickness of the negative photoresist was expressed as 1 nm when the thickness immediately after deposition was maintained even after development, and the multilayer molecular film photoresist formed using the Hf precursor was the most As it shows a normalized thickness of 1 nm at a low e-beam dose, it can be seen that the sensitivity is excellent.

FIG. 13a is a schematic diagram showing a form of irradiating EUV and a dose condition, and FIG. 13b is a photoresist obtained when irradiating EUV as shown in FIG. 13a to a photoresist using an Hf precursor formed using the method described with reference to FIG. 10 This is an optical photograph of a photoresist pattern. Specifically, FIG. 13a shows exposure by irradiating EUV as shown in FIG. 13a on a photoresist using the Hf precursor formed with reference to FIG. 10, and then in TMAH (Tetramethylammonium hydroxide) in H ₂ O for 2 minutes. This is a photograph developed by sonication.

Referring to FIGS. 13A and 13B, when a photoresist using an Hf precursor having a thickness of about 20 nm immediately after deposition is exposed using EUV, a thickness of about 10 nm or more when exposed and developed at a dose of about 40 mJ/cm ² or more. , which shows that the EUV sensitivity of the photoresist using the Hf precursor according to this experimental example is 40 mJ/cm ² .

FIG. 14a is an atomic force microscopy (AFM) image obtained after electron beam exposure and development of a photoresist using a Zn precursor formed by the method described with reference to FIG. 10, and FIG. 14b is an atomic force microscopy (AFM) image obtained after electron beam exposure and development of a PMMA photoresist. This is an AFM (Atomic force microscopy) image. At this time, the PMMA photoresist was coated with a solution in which PMMA was dissolved in chlorobenzene, and then irradiated with an electron beam, and the irradiated portion was removed by development to obtain a pattern. The electron beam irradiated to the two photoresists was commonly irradiated under conditions of a voltage of 100 kV, 100 pA, and a dose of 2500 uC/cm ² . The photoresist using the Zn precursor was ultrasonically treated in TMAH (Tetramethylammonium hydroxide) in H ₂ O for 2 minutes, and the unexposed portion was removed by development.

Referring to FIGS. 14A and 14B , it can be seen that the photoresist using the Zn precursor has lower edge roughness than the PMMA photoresist.

Claims

Equipped with a plurality of molecular lines extending in the upper direction of the substrate and arranged in a lateral direction,

Each molecular beam is a multilayer molecular film photoresist in which a plurality of inorganic single molecules and organic single molecules interposed between at least some of the inorganic single molecules are connected by bonds.
The method of claim 1,

A multilayer molecular film photoresist in which van der Waals interactions exist between the organic monomolecules in horizontally adjacent molecular lines among the molecular lines.
The method of claim 2,

The van der Waals interaction is a π-π bond multilayer molecular film photoresist.
The method of claim 1,

The multilayer molecular film photoresist of claim 1 , wherein each of the molecular lines is a combination of the inorganic single molecule and the organic single molecule that are alternately laminated.
The method of claim 1,

The inorganic monomolecules provided on the molecular lines are equally arranged in the transverse direction to form an inorganic monomolecular layer,

A multilayer molecular film photoresist in which inorganic monomolecules provided on the molecular lines are equally arranged in a transverse direction to form an organic monomolecular layer.
The method of claim 5,

The multilayer molecular film photoresist is a multi-layered layer having at least one of a light absorbing layer including light absorbing inorganic single molecules, a photoreactive layer including photoreactive inorganic single molecules, and an etch-resistant layer including etch-resistant inorganic single molecules. Molecular film photoresist.
The method of claim 6,

The multilayer molecular film photoresist wherein the light-absorbing inorganic molecules are inorganic molecules having a metal element having a d orbital.
The method of claim 7,

The metal element is Sn, Sb, Te, or Bi multilayer molecular film photoresist.
The method of claim 6,

The multilayer molecular film photoresist wherein the photoreactive inorganic molecules are inorganic molecules having a metal element of Zr, Al, Hf, Zn, or In.
The method of claim 6,

The etch-resistant inorganic single molecule is an inorganic single molecule having a metal element of Al, Ti, W, Zn, or Cu multilayer molecular film photoresist.
Equipped with a plurality of molecular lines extending in the upper direction of the substrate and arranged in a lateral direction,

Each of the molecular lines is a multilayer molecular film photoresist having a layer represented by Formula 1 below:

[Formula 1]

In Formula 1, one of * 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 single molecule containing a metal element,

OM is an organic monomer,

m is 1 to 2, n is 1 to 2, and l is 1 to 1000.
The method of claim 11,

The organic single molecule is a multilayer molecular film photoresist represented by Formula 3 below:

[Formula 3]

In Formula 3, one of the * 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 );

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 above aromatic ring, Z 3 and Z 4 are independently of each other a bond or a C1 to C5 substituted or unsubstituted and linear or branched alkylene group,

When MR is the above alkylene group, Z 3 and Z 4 are bonds.
The method of claim 11,

M includes a light-absorbing inorganic single molecule containing a metal element having d orbital, a photoreactive inorganic single molecule including Zr, Al, Hf, Zn, or In, or Al, Ti, Cu, W, or Zn A multilayer molecular film photoresist that is an inorganic monomolecule that is resistant to etching.
The method of claim 11,

The layer represented by Formula 1 is a multilayer molecular film photoresist layer represented by Formula 1A below:

[Formula 1A]

In Formula 1A, one of * 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,

M1 is a light-absorbing inorganic single molecule containing a metal element having a d orbital,

O1 is an organic monomer,

m1 is 1 to 2, n1 is 1 to 2, and l1 is 1 to 1000.
The method of claim 14,

Each of the molecular lines is a multilayer molecular film photoresist having a layer represented by the following Chemical Formula 1B above or below the layer represented by the Chemical Formula 1A:

[Formula 1B]

In Formula 1B, one of * 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,

M2 is a photoreactive inorganic single molecule containing Zr, Al, Hf, Zn, or In;

O2 is an organic monomer,

m2 is 1 to 2, n2 is 1 to 2, and l2 is 1 to 1000.
The method of claim 14,

Each of the molecular lines is a multilayer molecular film photoresist having a layer represented by the following Chemical Formula 1C above or below the layer represented by the Chemical Formula 1A:

[Formula 1C]

In Formula 1C, one of the * 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 etch-resistant inorganic monomolecule containing Al, Ti, Cu, W, or Zn;

O3 is an organic monomer,

m3 is 1 to 2, n3 is 1 to 2, and l3 is 1 to 1000.
According to claim 1 or claim 11,

The multilayer molecular film photoresist is a multilayer molecular film photoresist for EUV.
A multilayer molecular film photoresist having a layer represented by Chemical Formula 1 is prepared by providing a plurality of molecular lines each extending in the upper direction of the substrate and disposed in a transverse direction,

The layer represented by Chemical Formula 1 is formed by performing a plurality of cycles including forming a metal monomolecular layer and forming an organic molecular layer on a substrate. Multilayer molecular film photoresist deposition equipment:

[Formula 1]

In Formula 1, one of * 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 single molecule containing a metal element,

OM is an organic monomer,

m is 1 to 2, n is 1 to 2, and l is 1 to 1000.
The method of claim 18

M includes a light-absorbing inorganic single molecule containing a metal element having d orbital, a photoreactive inorganic single molecule including Zr, Al, Hf, Zn, or In, or Al, Ti, Cu, W, or Zn A multi-layer molecular film photoresist deposition equipment, which is an inorganic monomolecule that is resistant to etching.
The method of claim 18

The organic single molecule is a multilayer molecular film photoresist deposition equipment represented by the following formula (3):

[Formula 3]

In Formula 3, one of the * 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 );

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 above aromatic ring, Z 3 and Z 4 are independently of each other a bond or a C1 to C5 substituted or unsubstituted and linear or branched alkylene group,

When MR is the above alkylene group, Z 3 and Z 4 are bonds.