Multilayer molecular film photoresist having molecular line structure containing organic monomer with cross-linking functional group and manufacturing method thereof

Abstract

A multilayer molecular film photoresist is provided. The multilayer molecular film photoresist comprises a plurality of molecular lines which extend upwards from the substrate and are transversely arranged. Each molecular line comprises linearly linked monomers represented by the following Chemical Formula 1: [In Chemical Formula 1, one of * is a bond linked to a functional group in the lower monomer, and the other is a bond linked to a functional group in the upper monomer; oM is an organic monomer; mM is a primary inorganic monomer comprising a metal atom; m is 1-2, n is 1-2, and l is 1-1000. A side inorganic monomer including a metal atom is located between the molecular lines, and is bonded to a side surface of the organic monomer (OM) in one of the molecular lines. A cross-linking functional group is bonded to the side of the organic monomer (OM) in the other of the molecular lines.

Description

Technical Field

[0001] This invention relates to a photoresist, and more specifically, to a photoresist for EUV. Background Technology

[0002] Research on photoresists has been ongoing, particularly on methods for preparing liquid photoresists and then depositing them onto substrates via spin coating. Traditional photoresists primarily utilize chemically amplified photoresists (CARs) containing polymer resins, PAG (Photo-Acid Generator), and alkali (quencher).

[0003] In recent years, the semiconductor industry has been introducing extreme ultraviolet (EUV) lithography technology, which uses EUV light sources capable of forming ultra-fine patterns of 10 nm or smaller.

[0004] However, EUV has a lower photon density, only 1 / 14, compared to deep ultraviolet (DUV) at 193 nm, thus it is capable of generating random defects, particularly photon shot noise. For example, in the case of CAR, the low photon density leads to a low probability of PAG participating in the reaction, which can generate shot noise. Furthermore, a known disadvantage of CAR is that it exhibits relatively large line edge roughness due to the size of the polymer resin particles being larger than 4 nm. Summary of the Invention

[0005] [Technical Issues]

[0006] Therefore, the problem to be solved by the present invention is to provide a photoresist with excellent photon absorption and low line edge roughness and a method for preparing the same.

[0007] The technical problems of the present invention are not limited to those described above, and other unmentioned technical problems will be clearly understood by those skilled in the art through the following description.

[0008] [Technical Solution]

[0009] According to one embodiment of the present invention, a multilayer molecular film photoresist is provided. The multilayer molecular film photoresist comprises a plurality of molecular lines extending upward from a substrate and arranged laterally. Each molecular line comprises linearly connected monomers represented by the following chemical formula 1:

[0010] [Chemical Formula 1]

[0011]

[0012] In the chemical formula 1, one of the * is a bond connected to the functional group in the monomer below, and the other is a bond connected to the functional group in the monomer above. OM is an organic monomer, MM is a main inorganic monomer containing a metal atom, m is 1 to 2, n is 1 to 2, and l is 1 to 1000.

[0013] The inorganic monomer containing the metal atom is located between the molecular lines and is bonded to the side of the organic monomer (OM) in one of the molecular lines. The cross-linking functional group is bonded to the side of the organic monomer (OM) in the other molecular line.

[0014] Van der Waals interactions can exist between organic monomers within laterally adjacent molecular lines.

[0015] The main inorganic monomer can be represented by the following chemical formula 2:

[0016] [Chemical Formula 2]

[0017]

[0018] In the chemical formula 2, one of the * can be a bond connected to a functional group in the lower monomer, and the other can be a bond connected to a functional group in the upper monomer. a It can be O, S, Se, NR (R is H or CH3) or PR (R is H or CH3). M 0 It is a metal atom, and M 0 It can be Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W, or Si. Z1 and Z2 can be independently of each other a direct bond, a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylene oxide having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylene amino having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylene silylamino having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylene thio having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylene seleno having 1 to 20 carbon atoms, or a substituted or unsubstituted straight-chain or branched alkylene phosphino having 1 to 20 carbon atoms. a With L bThey can be halogen groups, C1 to C5 alkyl groups, C1 to C5 alkylsilamido groups, C1 to C5 alkoxy groups, C1 to C5 alkylthio groups, C1 to C5 alkylseleno groups, C1 to C5 alkylamino groups, C1 to C5 alkylphosphino groups, acetate groups, or aryloxy groups, independently of each other. The sum of na and nb can be an integer between 0 and 4. In one example, na and nb can both be 0.

[0019] The inorganic monomer on the side can be represented by the following chemical formula 3:

[0020] [Chemical Formula 3]

[0021]

[0022] In chemical formula 3, * can be a bond connected to an organic monomer. c It can be O, S, Se, NR (R is H or CH3) or PR (R is H or CH3). M 0 It is a metal atom, and M 0 It can be Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W, or Si. Z1 and Z2 can be independently of each other a direct bond, a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched oxoalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylsilylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylseleno group having 1 to 20 carbon atoms, or a substituted or unsubstituted straight-chain or branched alkylphosphin group having 1 to 20 carbon atoms. L a With L b They can be halogen groups, C1 to C5 alkyl groups, C1 to C5 alkylsilamido groups, C1 to C5 alkoxy groups, C1 to C5 alkylthio groups, C1 to C5 alkylseleno groups, C1 to C5 alkylamino groups, C1 to C5 alkylphosphino groups, acetate groups, or aryloxy groups, independently of each other. The sum of na and nb can be an integer between 0 and 4. R b2 It can be a halogen group (e.g., Cl, Br, or I), C1 to C5 alkyl, C1 to C5 alkylsilylamino, C1 to C5 alkoxy, C1 to C5 alkylthio, C1 to C5 alkylselenyl, C1 to C5 alkylamino, or C1 to C5 alkylphosphinyl. In one example, na and nb can both be 0.

[0023] The crosslinking functional group can be *-Z5X c R a3* can be a bond connected to an organic monomer. Z5 can be a direct bond, or a substituted or unsubstituted, straight-chain or branched C1 to C5, especially C1 to C3, alkylene groups. X c It can be O, S, Se, NR (where R is H or CH3) or PR (where R is H or CH3). R a3 It can be hydrogen or C1 to C2 alkyl.

[0024] The organic monomer can be represented by the following chemical formula 4:

[0025] [Chemical Formula 4]

[0026] *-X b -Z3-MR-Z4-*

[0027] In the chemical formula 4, one of the * can be a bond connected to a functional group in the lower monomer, and the other can be a bond connected to a functional group in the upper monomer. b It can be O, S, Se, NR (R is H or CH3) or PR (R is H or CH3). Z3 and Z4 can be directly bonded or straight-chain or branched alkylene groups having C1 to C5 independently. MR can be a host with a straight chain having 2 to 7 carbons or a non-aromatic or aromatic ring having 3 to 18 carbons. The side inorganic monomer or the crosslinking functional group can be bonded to the host (MR). In one example, MR can be a straight-chain alkylene group having C2 to C6.

[0028] According to another embodiment of the present invention, a multilayer molecular film photoresist is provided. The multilayer molecular film photoresist includes a plurality of molecular lines extending upward from a substrate and arranged laterally. Each molecular line contains linearly connected monomers, wherein each monomer comprises a plurality of host inorganic monomers containing metal atoms and organic monomers connected between at least a portion of the host inorganic monomers. Side inorganic monomers containing metal atoms are located between the molecular lines and bonded to the sides of the organic monomers.

[0029] The primary inorganic monomer and the organic monomer located within the molecular line can be linked by a bond selected from -O-, -S-, -Se-, -NR- (R is H or CH3), and -PR- (R is H or CH3) contained in either of these monomers. The organic monomer and the secondary inorganic monomer can also be linked by a bond selected from -O-, -S-, -Se-, -NR- (R is H or CH3), and -PR- (R is H or CH3) contained in either of these monomers.

[0030] The metal atoms contained in the main inorganic monomer or the side inorganic monomer can be Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Ti, Cu, W, or Si. Van der Waals interactions may exist between organic monomers within laterally adjacent molecular lines. Each molecular line can be formed by alternating stacking of the main inorganic monomer and the organic monomer. The multilayer molecular film photoresist can be a photoresist for EUV.

[0031] According to another embodiment of the present invention, a method for manufacturing a photoresist pattern is provided. A multilayer molecular film photoresist is provided. The multilayer molecular film photoresist includes a plurality of molecular lines extending upward from a substrate and arranged laterally. Each molecular line includes linearly connected monomers represented by the following chemical formula 1:

[0032] [Chemical Formula 1]

[0033]

[0034] In chemical formula 1, one of the asterisks represents a bond connected to a functional group in the monomer below, and the other represents a bond connected to a functional group in the monomer above. OM represents an organic monomer. MM represents a main inorganic monomer containing a metal atom. m is 1 to 2, n is 1 to 2, and l is 1 to 1000.

[0035] The inorganic monomer containing the metal atom is located between the molecular lines and is bonded to the side of the organic monomer (OM) in one of the molecular lines. The cross-linking functional group is bonded to the side of the organic monomer (OM) in the other molecular line.

[0036] A portion of the multilayer molecular film photoresist is irradiated with an electron beam or EUV radiation to crosslink the inorganic monomer molecules with the crosslinkable functional groups. The unexposed portions of the multilayer molecular film photoresist are developed and removed.

[0037] According to another embodiment of the present invention, a method for manufacturing a photoresist pattern is provided. The method includes: loading a substrate into a chamber having a gas inlet and a gas outlet; performing an organic precursor sub-cycle; the organic precursor sub-cycle comprising supplying an organic precursor of chemical formula 5 into the chamber with the gas outlet closed, reacting the organic precursor on the substrate, and then purging any residual reaction gas in the chamber; performing an inorganic precursor sub-cycle; the inorganic precursor sub-cycle comprising supplying an inorganic precursor of chemical formula 6 into the chamber with the gas outlet closed, reacting the inorganic precursor on the organic precursor, and then purging any residual reaction gas in the chamber; performing multiple unit cycles including the organic precursor sub-cycle and the inorganic precursor sub-cycle to form a multilayer molecular film photoresist; irradiating a portion of the multilayer molecular film photoresist with an electron beam or EUV radiation; and developing and removing regions of the multilayer molecular film photoresist that are not exposed to radiation.

[0038] [Chemical Formula 5]

[0039]

[0040] In the chemical formula 5, R a1 R a2 and R a3 Each is independently hydrogen or a C1 to C2 alkyl group. X a X b and X c Each is independently O, S, Se, NR (R is H or CH3) or PR (R is H or CH3). Z3, Z4, and Z5 are independently C1 to C3 alkylene groups, either directly bonded or substituted or unsubstituted, either straight-chain or branched. MR is a straight-chain group having 2 to 7 carbons or a non-aromatic or aromatic ring group having 3 to 18 carbons. x is 1 or 2.

[0041] [Chemical Formula 6]

[0042]

[0043] In the chemical formula 6, R b1 With R b2 Each of the following groups is independently a halogen group, a C1 to C5 alkyl group, a C1 to C5 alkylsilamido group, a C1 to C5 alkoxy group, a C1 to C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamido group, or a C1 to C5 alkylphosphino group. 0The elements are Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W, or Si. Z1 and Z2 are independently of each other a direct bond, a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched oxoalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylsilylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylseleno group having 1 to 20 carbon atoms, or a substituted or unsubstituted straight-chain or branched alkylphosphin group having 1 to 20 carbon atoms. L a With L b Each of the following groups is independently a halogen group, a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkylthio group, a C1 to C5 alkylseleno group, a C1 to C5 alkylamino group, a C1 to C5 alkylphosphinyl group, an acetate group, or an aryloxy group. The sum of na and nb is an integer between 0 and 4.

[0044] [Beneficial Effects]

[0045] When the multilayer molecular film photoresist according to one embodiment of the present invention is exposed and developed, molecular lines (rather than particles) can be separated. Therefore, the line edge roughness (LER), which represents the side roughness of the pattern, can be reduced, and the resolution can also be improved.

[0046] Furthermore, the multilayer molecular film photoresist contains, for example, metal atoms with extremely high absorption coefficients for EUV, enabling it to exhibit high photosensitivity and low random failure rate even under EUV conditions with low photon density.

[0047] Furthermore, the multilayer molecular film photoresist includes side inorganic monomers containing metal atoms located between molecular lines and bonded to the side of an organic monomer within one molecular line, as well as crosslinking functional groups bonded to the side of an organic monomer within the other molecular line. Upon irradiation, the unreacted terminal functional groups on the side inorganic monomers further react with the organic monomers, leading to crosslinking and thus forming a photoresist pattern with excellent etch resistance. Attached Figure Description

[0048] Figure 1 This is a schematic diagram illustrating a multilayer molecular film photoresist with a vertical molecular line structure according to an embodiment of the present invention.

[0049] Figure 2 This is a schematic diagram illustrating a multilayer molecular film photoresist with a vertical molecular line structure according to an embodiment of the present invention.

[0050] Figure 3 This is a schematic diagram illustrating an apparatus for manufacturing a multilayer molecular film photoresist having a vertical molecular line structure according to an embodiment of the present invention.

[0051] Figures 4 to 7 A schematic diagram illustrating the photolithography method according to an embodiment of the present invention is shown in sequence.

[0052] Figure 8 A multilayer molecular film photoresist with a vertical molecular line structure formed according to manufacturing example 1 is shown.

[0053] Figure 9 A graph showing the film growth rate based on the supply time of each precursor during the manufacturing of photoresist according to Manufacturing Example 1 is presented.

[0054] Figure 10 A graph showing the change in film thickness of the photoresist according to manufacturing example 1 as a function of the number of cycles, and an AFM image of the surface are shown.

[0055] Figure 11 SEM images of the photoresist obtained in Manufacturing Example 1 after patterning are shown.

[0056] Figure 12 To show Figure 11 A schematic diagram of the cross-linking of the photoresist during the exposure process.

[0057] Figure 13 A graph showing the electron beam sensitivity of the photoresist obtained in manufacturing Example 1.

[0058] Figure 14 A schematic diagram illustrating EUV irradiation patterns and dosage conditions, and Figure 15 For the photoresist used in manufacturing Example 1 Figure 14 An optical photograph of the photoresist pattern obtained after EUV pattern irradiation.

[0059] Figure 16 To show the graph of the change in film thickness of the photoresist according to manufacturing example 2 with the number of cycles and the AFM image of the surface.

[0060] Figure 17 To show the graph of the change in film thickness of the photoresist according to manufacturing example 3 with the number of cycles and the AFM image of the surface. Detailed Implementation

[0061] In this specification, "metal" can include all metals, but by way of example, it can be a transition metal, a post-transition metal, or a metalloid.

[0062] In this specification, radiation may be EUV or an electron beam, as an example. However, it is not limited to these in certain cases.

[0063] In this specification, monomer refers to a non-polymer molecule. By way of example, monomer refers to a small molecule, specifically a molecule having 100 or fewer atoms, and more specifically a molecule having 30 or fewer atoms.

[0064] In this specification, "molecules or functional groups connected by bonds" can refer to molecules or functional groups that are directly connected or indirectly connected by other molecules or functional groups placed between them.

[0065] In this specification, when “CX to CY” is written, it should be understood that all integers corresponding to the number of carbon atoms X to Y are also written. For example, when C1 to C10 are described, it should be understood that C1, C2, C3, C4, C5, C6, C7, C8, C9 and C10 have all been described.

[0066] In this specification, when “X to Y” is written, it should be understood that all integers between X and Y are also written. For example, when 1 to 10 is described, it should be understood that 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 have been described.

[0067] In this specification, when referred to as an "aromatic ring," it means a 5- to 12-membered, specifically 5- to 6-membered aromatic ring, having a homocyclic structure in which all constituent members are carbon, or a heterocyclic structure in which some constituent members are replaced by heteroelements.

[0068] The "alkylene" or "alkyl" used in this article may consist entirely of carbon elements forming the main chain, or some of the carbon may be replaced by O, S, N, C=O, or Si. The substituent elements are not limited to these.

[0069] Figure 1 This is a schematic diagram illustrating a multilayer molecular film photoresist with a vertical molecular line structure according to an embodiment of the present invention.

[0070] refer to Figure 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, a flexible substrate may be a polymer 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, may be formed on the substrate. The device may be an organic electronic device, such as an organic light-emitting diode or an organic solar cell. Therefore, in this embodiment, the substrate 10 may be a bare substrate, or a substrate containing a device formed on a bare substrate.

[0071] An etch target layer 20 can be formed on the substrate 10. The etch target layer 20 is a layer formed by etching using the photoresist pattern as an etch mask after a photoresist pattern has been formed on the layer 20, and can be formed from various materials used in semiconductor processes. As an example, the etch target layer 20 can be a metal film, a semiconductor film, an insulating film, or a composite film containing any of these. The metal film can be used to form wiring and can be aluminum, tungsten, titanium, or a composite film containing any of these. The semiconductor film can be a silicon film, such as a monocrystalline silicon film, a polycrystalline silicon film, an amorphous silicon film, or a composite film containing any of these. The insulating film can include inorganic insulating films, such as silicon oxide films or silicon nitride films; organic insulating films, such as amorphous carbon films; or composite films containing any of these. In one example, the etch target layer 20 can be a bare substrate.

[0072] The etched target layer 20 may have hydroxyl, thiol, amine or phosphine groups as examples of surface functional groups, or may be surface treated to have the same functional groups.

[0073] A multilayer molecular film photoresist 30 with a molecular line structure can be formed on the etch target layer 20. Specifically, the multilayer molecular film photoresist 30 can have multiple molecular lines ML, each extending upward from the substrate 10 and arranged laterally. In one example, the molecular lines ML can extend upward from the substrate 10, for example, in a direction perpendicular to the substrate 10, and the lateral direction of the lateral arrangement can be substantially parallel to the substrate surface.

[0074] Each molecular line ML may contain linearly connected monomers, and these monomers may contain multiple host inorganic monomers M1, M2, M3 containing metal atoms, and organic monomers O1, O2, O3 interposed between at least some of the host inorganic monomers. Such a multilayer molecular film photoresist 30 may be called an organic-inorganic multilayer molecular film photoresist. In this specification, a molecular line ML may be defined as a main chain, molecular chain, or chain formed by the linear connection of host inorganic monomers and organic monomers through bonds. The bonds may be covalent bonds or coordinate bonds.

[0075] In one example, it may also include lateral inorganic monomers (not shown) located between molecular lines ML and bonded to the sides of organic monomers O1, O2, O3. In this specification, this side may be a region intersecting the extension direction of the molecular line ML, specifically, a region intersecting the upward direction of the substrate and parallel to the substrate. The main inorganic monomer, or the main inorganic monomer and the organic monomer, may be connected to another monomer by a bond selected from one of the adjacent monomers, the bond being selected from -O-, -S-, -Se-, -NR- (R is H or CH3), and -PR- (R is H or CH3). Furthermore, the organic monomer and the lateral inorganic monomer may be connected to another monomer by a bond selected from -O-, -S-, -Se-, -NR- (R is H or CH3), and -PR- (R is H or CH3) contained in either monomer. However, the invention is not limited thereto; monomers may be indirectly connected by bonds using additional functional groups.

[0076] In this embodiment, the multilayer molecular film photoresist 30 can be formed using atomic layer deposition or molecular layer deposition, such that almost all molecular lines ML in the multilayer molecular film photoresist 30 can have substantially the same stacked structure. Therefore, the molecular lines ML in the multilayer molecular film photoresist 30 can have substantially identical inorganic monomers and substantially identical organic monomers located on the same horizontal plane. Thus, inorganic monomers located on the same horizontal plane of the molecular lines ML can form an inorganic monolayer in the horizontal direction; organic monomers located on the same horizontal plane of the molecular lines ML can form an organic monolayer in the horizontal direction.

[0077] Furthermore, molecular lines ML can be formed such that the gap D between adjacent molecular lines ML is sufficiently narrow, thereby allowing van der Waals interactions VI to occur between the organic monomers O1, O2, and O3 within adjacent molecular lines ML. Van der Waals interactions VI can stabilize laterally adjacent molecular lines ML, preventing pattern collapse even at high aspect ratios, and allowing the molecular lines ML to extend substantially perpendicular to the substrate 10. In one example, the van der Waals interactions can be interactions between alkylene groups provided in the organic monomers O1, O2, and O3, or interactions between π-π bonds between aromatic groups.

[0078] The multilayer molecular film photoresist 30 may have the structure shown in the following chemical formula 1.

[0079] [Chemical Formula 1]

[0080]

[0081] In Formula 1, one of the * can be a bond connected to a functional group in the bottom layer or a functional group in the bottom monomer, and the other can be a bond connected to a functional group in the upper layer or a functional group in the upper monomer. This bond can be, for example, a covalent bond. In Formula 1, m can be 0 to 10, n can be 1 to 10, and l can be 1 to 10000, specifically 20 to 1000, more specifically 25 to 100. Specifically, m can be 1 to 2; for example, m can be 1. n can also be 1 to 2; for example, n can be 1. OM can be an organic monomer, and MM can be a main inorganic monomer. A detailed explanation of these will be provided later. Formula 1 can represent an organic monomer OM and a main inorganic monomer MM stacked sequentially on a bottom layer, or it can represent a main inorganic monomer MM and an organic monomer OM stacked sequentially on a bottom layer.

[0082] Figure 1 In this context, O1, O2, and O3 are all organic monomers OM; they can be different organic monomers or the same organic monomer. Furthermore, Figure 1 In this context, M1, M2, and M3 are all principal inorganic monomers (MM), which can be different inorganic monomers or the same inorganic monomer. Furthermore, in... Figure 1 In this formula, n1, n2, and n3 are independently equal to the n value defined in Formula 1, m1, m2, and m3 are independently equal to the m value defined in Formula 1, and l1, l2, and l3 are independently equal to the l value defined in Formula 1.

[0083] 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 etch-resistant layer FL3, which are distinguished according to the primary function of the host inorganic monomer (specifically, according to the primary function of the metal atoms provided in the host inorganic monomer). As an example, the multilayer molecular film photoresist 30 may include one, two, or three types of these layers. The stacking order of the light-absorbing layer FL1, the photoreactive layer FL2, and the etch-resistant layer FL3 may vary depending on the type of the etch target layer 20 and / or the type of pattern to be formed by photolithography. Simultaneously, the light-absorbing layer FL1, the photoreactive layer FL2, and the etch-resistant layer FL3 can all substantially undergo secondary electron generation and photoreaction based on light absorption.

[0084] Figure 2 This is a schematic diagram illustrating a multilayer molecular film photoresist with a vertical molecular line structure according to an embodiment of the present invention.

[0085] refer to Figure 2 The molecular lines ML of the multilayer molecular film photoresist 30 may include linearly connected main inorganic monomers and organic monomers represented by chemical formula 1; in some cases, the molecular lines ML may include linearly connected main inorganic monomers and organic monomers represented by chemical formula 2. Figure 2 In the chemical formula 1, l, m, and n are all 1, MM is represented by MX or MY, and OM is represented by OX or OY. The inorganic monomer MZ can be attached to the side of some organic monomers.

[0086] The primary inorganic monomer (MM, MX, or MY in Formula 1) can be a metal-containing inorganic monomer, specifically an organometallic monomer. As examples, the primary inorganic monomer can be a light-absorbing inorganic monomer containing a metal element with d orbitals, a photoreactive inorganic monomer containing Zr, Al, Hf, Zn, or In, or an etch-resistant inorganic monomer containing Al, Ti, Cu, W, Si, or Zn. The metal element with d orbitals (specifically 4d or 5d orbitals) can be Sn, Sb, Te, or Bi. Although inorganic monomers are classified according to different functions, all described inorganic monomers can possess both light absorption and photoreactivity capabilities.

[0087] Specifically, the main inorganic monomers MM, MX, and MY can be organometallic monomers having at least two organic functional groups or ligands, and can be bonded directly or indirectly to one end by a connector X. a (For example, O, S, Se, NR (R is H or CH3) or PR (R is H or CH3)) are bonded to the lower or bottom monomer (specifically, the organic monomer OM). The main inorganic monomers MM, MX, and MY can be organometallic monomers represented by the following chemical formula 2.

[0088] [Equation 2]

[0089]

[0090] In Formula 2, * one of them can be a bond connected to a functional group in the bottom layer or to an organic or inorganic monomer (specifically, its functional group) at the bottom, and the other can be a bond connected to a functional group in the upper layer or to an organic or inorganic monomer (specifically, its functional group) above. The bond can be, for example, a covalent bond. Z1 and Z2 can be independently of each other a bond, a substituted or unsubstituted straight-chain or branched C1 to C20 alkylene group, a substituted or unsubstituted straight-chain or branched C1 to C20 oxoalkylene group, a substituted or unsubstituted straight-chain or branched C1 to C20 alkylamino group, a substituted or unsubstituted straight-chain or branched C1 to C20 alkylsilylamino group, a substituted or unsubstituted straight-chain or branched C1 to C20 alkylthio group, a substituted or unsubstituted straight-chain or branched C1 to C20 alkylselenyl group, or a substituted or unsubstituted straight-chain or branched C1 to C20 alkylphosphinyl group. M 0 It can be a light-absorbing metal atom with d orbitals; a photoreactive metal atom of Zr, Al, Hf, Zn, or In; or an etch-resistant metal atom of Al, Ti, Cu, W, or Zn. Metal elements with d orbitals (specifically 4d or 5d orbitals) can be Sn, Sb, Te, or Bi. X aIt can be O, S, Se, NR (R can be H or CH3) or PR (R can be H or CH3).

[0091] L a With L b Is with M 0 Bonded functional groups. L a With L b The quantity, the sum of na and nb, can be determined by M. 0 The maximum coordination number is determined by the sum of na and nb, and can be less than or equal to that maximum coordination number minus 2 (this value takes into account Z1 and Z2). For example, the sum of na and nb can be an integer between 0 and 4. a With L b The groups can be halogenated (e.g., Cl, Br, or I), C1 to C5 alkyl, C1 to C5 alkylsilylamino, C1 to C5 alkoxy, C1 to C5 alkylthio, C1 to C5 alkylselenyl, C1 to C5 alkylamino, or C1 to C5 alkylphosphinyl, independently of each other. The C1 to C5 alkyl groups can be substituted or unsubstituted straight-chain or branched alkyl groups. Furthermore, in Formula 2, when na and / or nb are 2 or greater, L... a and / or L b They can be chosen independently from the examples above. In one example, when the sum of na and nb is 2 or greater, L a With L b The two M that can be connected to them 0 They combine to form heterocyclic or heteroaryl groups. Z1, Z2, L a or L b With M 0 Each bond can be either a covalent bond or a coordinate bond, independent of each other.

[0092] refer to Figure 2 M X and M Y Corresponding to M in chemical formula 2 0 The primary inorganic monomer MX is an exemplary representation of the case where both na and nb are 0 and Z1 and Z2 are direct bonds. Similarly, the primary inorganic monomer MY is an exemplary representation of the case where both na and nb are 1 and Z1 and Z2 are direct bonds.

[0093] The inorganic monomer MZ can be represented by the following chemical formula 3.

[0094] [Chemical Formula 3]

[0095]

[0096] In chemical formula 3, X c It can be O, S, Se, NR (where R is H or CH3) or PR (where R is H or CH3). In one example, Xc It can be S. R b2 It can be a halogen group (e.g., Cl, Br, or I), C1 to C5 alkyl, C1 to C5 alkylsilamido, C1 to C5 alkoxy, C1 to C5 alkylthio, C1 to C5 alkylseleno, C1 to C5 alkylamino, or C1 to C5 alkylphospho. Z1, Z2, L a L b ,na,nb and M 0 As defined in chemical formula 2. In some cases, R b2 L a With L b The two M that are directly or indirectly bonded to them 0 They can combine to form heterocyclic or heteroaryl groups. In some cases, R b2 Can be in the same position as M 0 The state of coordinate bonding. Figure 2 In the shown side inorganic monomer MZ, M Z Corresponding to M in chemical formula 3 0 This indicates the case where na and nb are both 0 and Z1 and Z2 are both direct bonds.

[0097] exist Figure 2 In the process, the Z1, Z2, and L of the main inorganic monomer MX bonded to the upper part of the organic monomer OX are... a L b ,na,nb and M 0 It can respectively bind to the Z1, Z2, and L of the inorganic monomer MZ that is bonded to the side of the organic monomer OX. a L b ,na,nb and M 0 The same. This can be attributed to the fact that the main inorganic monomer MX, which is bonded to the top of the organic monomer OX, and the side inorganic monomer MZ, which is bonded to the side of the organic monomer OX, are formed in the same step using the same metal precursor.

[0098] Organic monomers (OM in chemical formula 1, Figure 2 The OX and OY in formula 1 can have a straight chain containing 2 to 7 carbons or a non-aromatic or aromatic ring containing 3 to 18 carbons as its main body. Some carbons can be substituted by elements selected from C=O, N, S, O, and Si. The straight chain can extend in a direction substantially the same as the molecular line ML. The long axis of the ring can also extend in a direction substantially the same as the direction of extension of the molecular line ML. Organic monomers (OM in formula 1, Figure 2 The OX and OY groups in the matrix can be directly or indirectly bonded to the linker functional group X in the lower part of the matrix. b This connective functional group X bonds with the lower layer (specifically, the underlying inorganic monomer). bSpecifically, -O-, -S-, -Se-, -NR- (where R is H or CH3) or -PR- (where R is H or CH3).

[0099] In one example, some organic monomers (OM in Formula 1, Figure 2 The OX group in formula 2 can have an amide or amino group in the straight chain or ring. When the inorganic monomer (MZ in formula 2, where x is 1 or greater) is bonded to the organic monomer, the amide or amino group (which is -NR-, where R is H or CH3) can serve as the linking functional group X. c Metal atom M Z It can bond with this linker functional group. In another example, the crosslinking functional group (-Z5X) c R a3 Among them Figure 2 Z5 is a direct bond) or a side inorganic monomer (MZ, -Z5X) c M Z R b2 Among them Figure 2 Z5 (where Z5 is a direct bond) can react with organic monomers (OM in formula 1). Figure 2 The lateral bonding of the OX group in the structure. In this case, the connecting functional group X... c It can be O, S, Se, NR (where R is H or CH3) or PR (where R is H or CH3).

[0100] As an example, the organic monomer OM in Formula 1, and Figure 2 The OX and OY in the formula can be organic monomers represented by the following chemical formula 4:

[0101] [Chemical Formula 4]

[0102] *-X b -Z3-MR-Z4-*

[0103] In chemical formula 4, one of the asterisks (*) can be a bond connected to a functional group of a bottom-layer or lower monomer (e.g., the lower main inorganic monomer) in the molecular chain, and the other can be a bond connected to a functional group of an upper-layer or upper monomer (e.g., the upper main inorganic monomer). The bond can be, for example, a covalent bond. X b It can be O, S, Se, NR (where R is H or CH3) or PR (where R is H or CH3). In one example, X b With X a or X cCompared to other compounds, it can have higher reactivity, for example, it can be O or S. Z3 and Z4 can be directly bonded or straight-chain or branched C1 to C5 alkylene groups. Here, substitution can refer to the substitution of the hydrogen of the alkylene group by various functional groups, such as OH, SH, SeH, NR2 (where R is independently H or CH3) or PR2 (where R is independently H or CH3).

[0104] In one example, MR in Formula 4 can have a straight chain containing 2 to 7 carbons or a non-aromatic or aromatic ring containing 3 to 18 carbons as its body. Some carbons can be substituted by elements selected from C=O, N, S, O, and Si. The straight chain can be, for example, a straight-chain C3 to C7 alkylene, specifically a straight-chain C3 to C5 alkylene. The straight chain can be substituted by C1 to C2 alkyl groups. When MR is straight-chain, Z3 and Z4 can be direct bonds.

[0105] In one example, the crosslinking functional group -(Z5X) c R a3 ) x It can be MR-bonded with at least some organic monomers. Here, Z5 can be a direct bond or a substituted or unsubstituted, straight-chain or branched C1 to C5, especially C1 to C3, alkylene group. X c It can be O, S, Se, NR (where R is H or CH3) or PR (where R is H or CH3). In one example, X c It can be S. R a3 It can be hydrogen or C1 to C2 alkyl. In one example, Z5 can be a direct bond, in which case X c It can bond directly to MR. The value of x can be 1 to 2. Lateral functional group - Z5X c R a3 It can bond to carbon atoms within the MR, or to N or Si atoms included through carbon substitution. When multiple -Z5X c R a3 When groups are bonded to the same member of an MR, their number (x) may be limited by the number of covalent bonds available to that member. Figure 2 An example shows x being 1 and Z5 being in -(Z5X) c R a3 ) x In the case of a direct bond, MR can have either an amide or an amino group.

[0106] Furthermore, the inorganic monomer MZ represented by the above chemical formula 4 can bond with the MR of at least some organic monomers.

[0107] exist Figure 2 In the middle, OX is set in the first layer FL. X Organic monomers within, which are bonded with cross-linking functional groups (-(Z5X)c R a3 ) x An exemplary representation of an organic monomer, where x = 1 and Z5 is a direct bond, or a side inorganic monomer MZ. OY is disposed in the second layer FL. Y Organic monomers within, which are exemplary representations of organic monomers that are unbonded crosslinked functional groups or side inorganic monomers.

[0108] The multilayer molecular film photoresist 30 can have a structure in which inorganic monomers MM and organic monomers OM are alternately stacked. In this case, the organic monomers OM are alternately arranged between the inorganic monomers MM, so that the inorganic monomers MM and organic monomers OM can self-assemble. As a result, molecular lines ML can each extend relative to the substrate 10 in an upward direction, such as a vertical direction, while being arranged in a spaced-apart manner.

[0109] The van der Waals interaction VI between organic monomers OM within adjacent molecular lines ML can stabilize laterally adjacent molecular lines ML, preventing them from collapsing even if the pattern has a high aspect ratio.

[0110] Figure 3 This is a schematic diagram of an apparatus for manufacturing a multilayer molecular film photoresist having a vertical molecular line structure according to an embodiment of the present invention.

[0111] Also refer to Figure 2 and Figure 3 The substrate S can be mounted on a stage 102 within a chamber 100 having a gas inlet 120 and a gas outlet 140. The substrate S can be a reference. Figure 1 The substrate 10 on which the etched target layer 20 is formed.

[0112] Before loading the substrate S, the chamber 100 can be heated and maintained at the deposition temperature via the controller 150. The deposition temperature can be 20°C to 250°C, 50°C to 200°C, 80°C to 150°C, 90°C to 140°C, or 100°C to 130°C. The gas outlet 140 can be connected to a vacuum pump.

[0113] First, a vacuum can be created inside chamber 100 by closing all gas inlet valves 130, 132 and 134 connected to gas inlet 120 and opening gas outlet valve 142 connected to gas outlet 140.

[0114] Subsequently, it can be achieved by performing actions including forming the main inorganic monomer layer (MM in Formula 1, specifically...) Figure 2 The steps of (MX or MY in the formula) and the formation of organic monomer layers (OM in formula 1, specifically) Figure 2The process involves repeating the steps of (OX or OY) to form a multilayer molecular film photoresist 30. The steps of forming the inorganic monomer layer and the organic monomer layer can be performed using atomic layer deposition, specifically molecular layer deposition. This specification describes a unit cycle in which an inorganic monomer layer is formed after the organic monomer layer, but this concept should be interpreted to include: forming an organic monomer layer after the inorganic monomer layer is formed during the execution of the unit cycle.

[0115] In the formation of organic monomer layers (OM in chemical formula 1, specifically...) Figure 4 In the OX or OY step, an organic monomer layer unit cycle can be performed. The organic monomer layer unit cycle can include an organic precursor dosing step, which involves adding an organic precursor and chemically bonding it to the lower layer via self-assembly; and a purging step, which involves supplying a purging gas to purge unreacted organic precursors and reaction byproducts.

[0116] Organic precursors may have a linear chain with 2 to 7 members or a non-aromatic or aromatic ring with 3 to 18 members. The members can be selected from the group consisting of C, C=O, N, S, O, and Si. Organic precursors may have an OR ring directly or indirectly bonded to one end of the host. a1 SR a1 、SeR a1 NRR a1 (R can be H or CH3) or PRR a1 (R can be H or CH3), and OR directly or indirectly bonded to the other end of the host. a2 SR a2 、SeR a2 NRR a2 (R can be H or CH3) or PRR a2 (R can be H or CH3). R a1 and R a2 They can be hydrogen or C1 to C2 alkyl groups independently of each other. Furthermore, the organic precursor can have amide or amine groups within the straight chain or ring. In another example, the organic precursor may further include crosslinking functional groups, such as OR, on the side branches of its straight-chain body. a3 SR a3 、SeR a3 NRR a3 (R can be H or CH3) or PRR a3 (R can be H or CH3). R a3 It can be hydrogen or C1 to C2 alkyl.

[0117] In one example, the organic precursor can be represented by the following chemical formula 5.

[0118] [Chemical Formula 5]

[0119]

[0120] In chemical formula 5, R a1 and R a2 They can be hydrogen or C1 to C2 alkyl groups independently of each other, and X b and X a They can be O, S, Se, NR (R can be H or CH3) or PR (R can be H or CH3) independently of each other. As an example, X b It can be O or X a It can be S. Meanwhile, Z3, Z4, and MR are as defined in chemical formula 4 above.

[0121] -(Z5X c R a3 ) x As a crosslinking functional group, Z5 can be a direct bond or a substituted or unsubstituted, straight-chain or branched C1 to C5 (specifically C1 to C3) alkylene group. X c It can be O, S, Se, NR (where R is H or CH3) or PR (where R is H or CH3). In one example, X c It can be S. R a3 It can be hydrogen or C1 to C2 alkyl. In one example, Z5 can be a direct bond, in which case X c It can be directly bonded to MR. The value of x can be from 0 to 2. When x is from 1 to 2, the crosslinking functional group -Z5X c R a3 It can bond to members within the MR, specifically to C, N, or Si. If the crosslinking functional group -(Z5X) c R a3 ) x The number (x) of identical carbon atoms bonded to MR is limited by the number of available covalent bonds for that carbon. When n is 0 in Formula 2, the chain of MR can have amide or amine groups. In another example, when n is 0 in Formula 2, MR can consist of only carbon. Figure 2 It shows that x is 1 and Z5 is in -(Z5X) c R a3 ) x The middle section is an example of a direct key.

[0122] When x is 1 in chemical formula 5, or when x is 0 and an amide or amine group is provided as a reactive functional group in MR, examples of organic precursors can be as follows:

[0123]

[0124] In the case where x is 0 in formula 5 and no reactive functional group (e.g., amide or amine group) is provided in MR, examples of organic precursors can be as follows:

[0125]

[0126] In the above organic precursors, n can be 1 to 2.

[0127] During the organic precursor addition step, a reaction according to reaction scheme 1 below may occur.

[0128] [Reaction Scheme 1]

[0129]

[0130] In reaction scheme 1, R0 can be a functional group on the surface of the bottom layer or the monomer below, specifically the surface functional group of the main inorganic monomer below (R0 in reaction scheme 2 below). b2 R0 can be hydrogen, hydroxyl, thiol, amino, phosphin, C1 to C5 alkyl, C1 to C5 alkoxy, C1 to C5 alkylthio, C1 to C5 alkylselenyl, C1 to C5 alkylamine, or C1 to C5 alkylphosphinyl. a1 X b -Z3-MR(-Z5-X c R a3 ) x (-Z4-X a R a2 ) is an organic precursor, and its functional groups are as defined in the above cultural formula 5. When X b With X a When they differ, the more reactive functional group can bind to the underlying surface functional groups. As an example, when X... b With X a When O and S are respectively, O can bind to the surface functional groups of the underlying layer. X c It can also be with X b Compared to less reactive functional groups, it binds to the underlying surface functional groups, such as S.

[0131] Referring to reaction scheme 1 described above, the organic precursor can react with functional groups on the surface of the substrate, thereby self-assembling onto the substrate. During this process, R0R... a1 It may be generated as a reaction byproduct. Subsequently, in the purging step, the remaining excess organic precursor and the aforementioned reaction byproducts can be purged.

[0132] In the organic precursor addition step, the organic precursor can be supplied from the organic precursor storage unit 114 to the chamber 100 with the organic precursor control valve 134 open and the gas outlet valve 142 closed (organic precursor supply step). The organic precursor in the organic precursor storage unit 114 can be stored in a solid, liquid, or gaseous state. The organic precursor storage unit 114 can be heated, and the organic precursor can be supplied to the chamber 100 at a predetermined vapor pressure. In one embodiment, the organic precursor can be supplied without a carrier gas. In other words, only the organic precursor can be supplied to the chamber 100.

[0133] Because the organic precursor is supplied with the gas outlet valve 142 closed, the organic precursor may accumulate within chamber 100 and increase the pressure within chamber 100. The organic precursor may be supplied until the pressure in chamber 100 reaches the reaction pressure (organic precursor supply step). The reaction pressure can be the individual pressure of the organic precursor in chamber 100 and can be in the range of 10 mTorr to 10 Torr, specifically 50 mTorr to 10 Torr, 100 mTorr to 6 Torr, 130 mTorr to 3 Torr, or 150 mTorr to 1 Torr. Typically, the precursor is introduced into the chamber along with the carrier gas. Considering that the partial pressure of the precursor in this case is approximately 1 to 10 mTorr, an individual pressure of the organic precursor in chamber 100 greater than 50 mTorr may mean that the organic precursor may be under pressure in chamber 100.

[0134] When the reaction pressure is reached, the organic precursor control valve 134 can be closed, and the chamber is sealed for a predetermined period of time (organic precursor exposure step) simultaneously with the closure of the gas outlet valve 142. The organic precursor supply step and the organic precursor exposure step can be referred to as the organic precursor dosing step. However, the organic precursor exposure step can be omitted in some cases. During the organic precursor dosing step, the reaction according to reaction scheme 1 may occur.

[0135] Subsequently, chamber 100 can be purged (organic precursor purging step). Specifically, purge gas control valve 132 and gas outlet valve 142 are opened to allow purge gas in purge gas storage unit 112 to flow onto the substrate surface to remove unreacted excess organic precursors and reaction byproducts. The purge gas can be an inert gas, and inert gases may include, for example, argon (Ar), nitrogen (N2), or combinations thereof.

[0136] In the formation of inorganic monomer layers (MM in chemical formula 1, specifically...) Figure 4In the MX or MY step, a unit cycle can be performed. This unit cycle may include an inorganic precursor addition step, i.e., adding an inorganic precursor and chemically bonding it to the bottom layer by self-assembly; and a purging step, i.e., supplying a purging gas to purge unreacted inorganic precursors and reaction byproducts.

[0137] Inorganic precursors can be organometallic monomers having at least two organic functional groups or ligands. Inorganic precursors can be represented by the following chemical formula 6.

[0138] [Chemical Formula 6]

[0139]

[0140] In chemical formula 6, R b1 and R b2 Each of the following groups is independently a halogen group (e.g., Cl, Br, or I), a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkylthio group, a C1 to C5 alkylselenyl group, a C1 to C5 alkylamino group, or a C1 to C5 alkylphosphinyl group. The C1 to C5 alkyl groups can be substituted or unsubstituted straight-chain or branched alkyl groups. Z1, Z2, L a L b ,na,nb and M 0 As defined in chemical formula 2. Furthermore, in some cases, R... b1 R b2 L a and L b The two M that can be directly or indirectly bonded to them 0 Combining to form heterocyclic or heteroaryl groups. In some cases, R b1 and R b2 At least one of them can be in the same position as M 0 The state of coordination bonding.

[0141] As an example, Z1 and Z2 can be keys, L a L b R b1 and R b2 They can be the same functional group. As another example, Z1 and Z2 can be a bond, L a With L b They can be the same functional groups, and R b1 and R b2 They can be the same functional groups, but L a and R b1 These can be different functional groups.

[0142] Examples of the aforementioned inorganic precursors are shown below.

[0143]

[0144]

[0145]

[0146] In the aforementioned metal precursors, dmamp refers to 1-dimethylamino-2-methyl-2-propoxy, and R1, R2, R3 and R4 can each be independently C1 to C5 alkyl groups.

[0147] In the inorganic precursor addition step, with the inorganic precursor gas control valve 130 open and the gas outlet valve 142 closed, inorganic precursor gas can be supplied from the inorganic precursor storage unit 110 to the chamber 100 (inorganic precursor supply step). The inorganic precursor in the inorganic precursor storage unit 110 can be stored in a solid, liquid, or gaseous state. The inorganic precursor storage unit 110 can be heated to below the thermal decomposition temperature of the inorganic precursor, thereby supplying the inorganic precursor to the chamber 100 at a predetermined vapor pressure. The inorganic precursor can be supplied without a carrier gas. In other words, only the inorganic precursor can be supplied to the chamber 100.

[0148] Because the inorganic precursor is supplied with the gas outlet valve 142 closed, the inorganic precursor may accumulate within chamber 100 and increase the pressure within chamber 100. The inorganic precursor may be supplied until the pressure in chamber 100 reaches the reaction pressure (inorganic precursor supply step). This reaction pressure can be the pressure of the inorganic precursor alone in chamber 100, ranging from 10 mTorr to 10 Torr, specifically 50 mTorr to 10 Torr, 100 mTorr to 6 Torr, 600 mTorr to 5 Torr, or 700 mTorr to 2 Torr. Typically, the precursor is added to the chamber along with the carrier gas. Considering that the partial pressure of the precursor in this case is approximately 1 mTorr, a pressure of 50 mTorr or higher for the inorganic precursor alone in chamber 100 indicates that the inorganic precursor may be under pressure.

[0149] When the reaction pressure is reached, the organic precursor control valve 134 can be closed, sealing the chamber for a predetermined period of time (inorganic precursor exposure step). The inorganic precursor supply step and the inorganic precursor exposure step can be referred to as the inorganic precursor addition step. However, the inorganic precursor exposure step can be omitted in some cases. In the inorganic precursor addition step, the reaction according to reaction scheme 2 may occur, and in some cases, the reactions according to both reaction scheme 2 and reaction scheme 3 may occur.

[0150] Subsequently, chamber 100 can be purged (inorganic precursor purging step). Specifically, the purge gas control valve 132 and gas outlet valve 142 are opened to allow the purge gas in the purge gas storage unit 112 to flow to the substrate surface inside the chamber, in order to remove excess inorganic precursor gas and reaction byproducts that are not adsorbed on the substrate surface. The purge gas is an inert gas, and the inert gas may include, for example, argon (Ar), nitrogen (N2), or a combination thereof.

[0151] During the inorganic precursor addition step, the following reaction according to reaction scheme 2 may occur.

[0152] [Reaction Scheme 2]

[0153]

[0154] In reaction scheme 2, *-X a R a2 The underlying surface functional groups are specifically the surface functional groups of the previously formed organic monomer OM. The inorganic precursor in Formula 6 can react with the surface functional groups of the previously formed organic monomer OM, thereby self-assembling onto the surface of the organic monomer OM. In this process, R... a2 R b1 It may be generated as a reaction byproduct. Subsequently, in a purging step, the remaining inorganic precursor and the aforementioned reaction byproducts can be purged. In reaction scheme 2, the functional groups can be the same as those defined in reaction scheme 1 and chemical formula 6.

[0155] In another example of the inorganic precursor addition step, in addition to the reaction according to reaction scheme 2, a reaction according to reaction scheme 3 may also occur. When the organic precursor used in the step of forming the organic molecular layer OM further comprises a crosslinking functional group -Z5X on its side... c R a3 This situation may occur when x in chemical formula 5 is 1 or greater.

[0156] [Reaction Scheme 3]

[0157]

[0158] In reaction scheme 3, *-X c R a3 This can be a functional group located on the side of the organic monomer within the previously formed organic molecular layer OM, i.e., a crosslinking functional group. The inorganic precursor from Formula 6 supplied during the inorganic precursor addition step can react with this crosslinking functional group and be placed between the organic monomers within the organic molecular layer OM. In this process, R... a3 R b1It may be generated as a reaction byproduct. Subsequently, during the purging step, the remaining inorganic precursor and the byproducts (R) from reaction schemes 2 and 3 can be purged. a2 R b1 and R a3 R b1 In reaction scheme 3, the functional groups can be the same as those defined in chemical formulas 5 and 6.

[0159] However, this is not the only limitation. When the organic precursor used in the step of forming the organic molecular layer OM contains amide or amine groups within the alkylene chain constituting its main body, in reaction scheme 3, X... c It can be N, R a3 It can be hydrogen or C1 to C2 alkyl; specifically, -X c R a3 It can be -NH- or -NR a3 -

[0160] As an example, in the formation Figure 2 FL in X During the layering process, the organic precursor used further includes the crosslinking functional group -Z5X. c R a3 The organic precursor allows for the simultaneous occurrence of reactions schemes 2 and 3 during the inorganic precursor addition step. As a result, FL... X The upper organic monomer OX within the layer reacts with the inorganic precursor to bind the main inorganic monomer M. X (Reaction scheme 2), and some organic monomers OX can be crosslinked through the functional group -Z5X c R a3 It reacts with the inorganic precursor and binds to the lateral inorganic monomer MZ (reaction scheme 3), while the cross-linking functional group -Z5X of the other organic monomer OX... c R a3 It may remain without reacting with the inorganic precursor. Figure 2 In reaction scheme 2, M 0 Represented as M X M in reaction scheme 3 0 Represented as M Z Furthermore, although the figure shows ligand L... a With L b Not with M X Bonding, but not limited to this, na units of L a and nb units of L b Can be used with M X Bonding. Furthermore, although Z1, Z2, Z3, Z4, and Z5 in the chemical formula and reaction equation... Figure 2 It is displayed as a key, but is not limited to this.

[0161] Meanwhile, FL Y The organic monomer OY in the layer can be an organic monomer formed by performing reaction scheme 1 (x is 0) using an organic precursor that does not contain crosslinking functional groups. Specifically, it is an organic precursor with x being 0 in formula 5 and not having reactive functional groups in the host MR. In this case, only the reaction scheme 2 can occur when forming the inorganic monolayer MY. In the figure, na and nb in formula 6 and reaction scheme 2 are both 1, but the invention is not limited thereto.

[0162] In addition, although Figure 2 FL was formed at the same time. X Layers and FL Y Layers, but not limited to these, and may only form FL X Layer. When the organic monomer OY is formed, it reacts with FL. X Unlike the primary inorganic monomer MX in the layer, the secondary inorganic monomer MZ may not have enough space to participate in the reaction with the subsequently added organic precursor, and may remain with M. Z bonded -R b2 Bond. This also applies to FLs formed only sequentially. X Layer time.

[0163] The control unit 150 can control the opening and closing of the valve and the temperature of the chamber.

[0164] In this way, the reaction described in reaction scheme 1 above can be carried out in a pressurized environment with only the organic precursor at a pressure of 50 mTorr or higher (specifically 100 mTorr or higher). In this case, the organic precursor can react densely on the substrate, allowing the chains of the organic precursor to align upwards relative to the substrate 10, for example, in a vertical direction. Furthermore, the reaction described in reaction scheme 1 above can be carried out with the gas outlet valve 142 closed, specifically in a pressurized stagnant environment rather than a laminar flow environment. In this case, the dense reaction of the organic precursor on the substrate can be carried out more efficiently. However, the invention is not limited thereto; the organic precursor can be supplied separately without the use of a carrier gas when the gas outlet valve 142 is open, thereby allowing the reaction to proceed in a laminar flow state within the chamber.

[0165] According to one embodiment of the present invention, a molecular layer deposition apparatus can perform multiple cycles, which includes the steps of forming a primary inorganic monolayer (MM of chemical formula 1) and forming an organic molecular layer (OM of chemical formula 1), specifically the number of times represented by l in chemical formula 1.

[0166] When the first primary inorganic monolayer MX or the second primary inorganic monolayer MY is composed of multiple primary inorganic monolayers (n is 2 or greater in Formula 1), a unit cycle can be repeatedly executed. This unit cycle includes: an inorganic precursor addition step and a purging step according to reaction scheme 2 (or both reaction scheme 2 and reaction scheme 3) described above; a reaction gas addition step for adding a reaction gas to react with the inorganic precursor chemically bonded to the lower layer; and a purging step for supplying a purging gas to purge unreacted reaction gas and reaction byproducts. In this case, the reaction gas can be a hydrogen- or oxygen-containing gas (e.g., O2, O3, H2O), a nitrogen-containing gas (e.g., NH3), etc.

[0167] Figure 2 and Figures 4 to 7 A schematic diagram illustrating the photolithography method according to an embodiment of the present invention is shown in sequence.

[0168] For reference Figure 2 As described above, a multilayer molecular film photoresist 30 can be formed.

[0169] refer to Figure 4 A portion of the multilayer molecular film photoresist 30 can be irradiated using radiation, specifically EUV or an electron beam (Ebeam). EUV can have a wavelength of 13.5 nm. In this case, the metal atoms M within the main inorganic monomers, such as the first main inorganic monomer MX, the second main inorganic monomer MY, and the side inorganic monomer MZ... X M Y Or M Z It can absorb radiation and generate secondary electrons.

[0170] These secondary electrons can form crosslinks between adjacent molecular lines ML. Specifically, the unreacted functional group -R of the inorganic monomer MZ b2 It can crosslink with the remaining crosslinking functional group -X of the first organic monomer OX. c R a3 The reaction produces R. b2 R a3 As a reaction byproduct, the metal atoms M of the inorganic monomer MZ are also present. Z -X is formed between the main MR of the first organic monomer OX and the 0. c -key.

[0171] Furthermore, the first primary inorganic monomer MX corresponds to the case where both na and nb in chemical formula 2 are 0. In this case, M X It can be with X in other adjacent molecular lines a and / or X bBonding, specifically, forming coordinate bonds CB. The second main inorganic monomer MY corresponds to the case in chemical formula 3 where both na and nb are 1, in which case the M provided by other adjacent molecular lines... Y -L a With L b -M Y M can be formed Y -YM Y Key. Here, Y can be O, S, Se, N, or P.

[0172] These M Y -YM Y Key, M X With X a and / or X b The key between them, and M Z -X c -MR bonds are crosslinks formed through exposure and may not be etched by developer gas or developing plasma (as an example of a developer used to develop multilayer molecular film photoresist patterns formed through exposure).

[0173] refer to Figure 5 The multilayer molecular film photoresist 30, exposed to radiation, can be exposed to a developer. In this case, the developer can remove all regions formed between adjacent molecular lines ML except for cross-linked portions, thereby forming a multilayer molecular film photoresist pattern 31. The developer can be a developer solution, such as water, isopropanol (IPA), methyl isobutyl ketone (MIBK), or tetramethylammonium hydroxide (TMAH), or a developer gas, such as CF4, Ar, O2, or CHF3, or a plasma generated therefrom.

[0174] refer to Figure 6 The target film 20 can be etched using a multilayer molecular film photoresist pattern 31 as a mask. This etching can be, for example, plasma etching.

[0175] refer to Figure 7 This can remove the photoresist pattern 31 from multiple molecular films. This can be accomplished by ashing.

[0176] As described above, the multilayer molecular film photoresist 30 is formed by the self-assembly of inorganic and organic monomers linked by bonds within molecular lines. Therefore, molecular lines can grow upwards from the substrate independently without becoming entangled or tilted, and the molecular lines can be uniformly aligned in the lateral direction. The molecular lines can be formed so densely that van der Waals interactions VI can occur between organic molecules within adjacent molecular lines. Van der Waals interactions stabilize laterally adjacent molecular lines, thus preventing pattern collapse even at high aspect ratios. The dense formation of molecular lines may be attributed to the fact that the addition of organic and / or inorganic precursors is carried out without the use of a carrier gas, thereby increasing the pressure of the organic and / or inorganic precursors within the chamber. Therefore, the addition of organic and / or inorganic precursors can be carried out with the gas outlet of the chamber closed. In this case, the height of the unit layer can be approximately equal to the length of the unit layer, reflecting the actual size of the atoms within the unit layer and the actual length of the interatomic bonds.

[0177] In this way, the spacing between molecular lines ( Figure 1 or Figure 2 The D in the image can be very small, less than 1 nm, specifically less than 0.5 nm. Furthermore, by separating molecular lines rather than particles during exposure and development, the line edge roughness (LER), which refers to the roughness of the pattern edge, can be significantly reduced. For example, a very low line edge roughness of less than 1.2 nm can be achieved. Resolution can also be significantly reduced. For example, a resolution of less than 6 nm can be achieved. Moreover, the multilayer molecular film photoresist 30 contains light-absorbing inorganic monomers with inorganic atoms having extremely high light absorption coefficients for EUV, specifically metal atoms with 4d or 5d orbitals. Therefore, even for low photon density EUV, it can exhibit low random defects and high photosensitivity (e.g., 10 mJ / cm²). 2 ).

[0178] Furthermore, when the host organic precursor or monomer (MR in Formula 5) is a straight chain or a non-aromatic ring, the molecular lines can be formed more densely through van der Waals bonds between organic monomers within adjacent molecular lines. Additionally, when the cross-linking functional group -Z5X... c R a3 When carbon atoms, excluding the α-carbons adjacent to Z3 and Z5, are directly or indirectly bonded to the carbon atoms constituting the main MR in formula 5 and arranged between molecular lines, the gaps between organic monomers can be controlled to prevent them from becoming too narrow. Therefore, in the inorganic precursor addition step, the inorganic precursor can be introduced and crosslinked with the crosslinking functional group -Z5X located between molecular lines. c R a3As a result of the reaction, inorganic monomers can be positioned between molecular lines and bonded to them. However, due to insufficient space for introducing the organic precursor, the inorganic monomer may not react with the organic precursor in subsequent organic precursor addition steps, and may retain unreacted functional groups R at the ends. a3 The terminal unreacted functional group R of the inorganic monomer. a3 Under radiation, it reacts with organic monomers and crosslinks to form a photoresist pattern with excellent etch resistance.

[0179] The following is a preferred experimental example to aid in understanding the present invention. However, the following experimental example is only for the purpose of aiding in understanding the present invention, and the present invention is not limited to the following experimental example.

[0180] Manufacturing Example 1: Photoresist Manufacturing Example 1

[0181] Figure 8 This illustrates a multilayer molecular film photoresist with a vertical molecular line structure formed according to this manufacturing example.

[0182] refer to Figure 8 The substrate is loaded into a chamber equipped with a gas inlet and a gas outlet, and the substrate temperature is heated to 100°C. With the gas outlet closed, the organic precursor DMP (2,3-dimercaptopropanol) is supplied to the substrate through the gas inlet without a carrier gas until the chamber pressure reaches 200 mTorr (organic precursor supply step). Subsequently, the chamber inlet is also closed, the chamber pressure is maintained at 200 mTorr, and the organic precursor is reacted on the substrate for 1 second (organic precursor exposure step). Then, with both the gas inlet and gas outlet open, argon gas is supplied through the gas inlet as a purge gas for 600 seconds to purge reaction byproducts and residual reaction gases (organic precursor purging step). The organic precursor supply step, the organic precursor exposure step, and the organic precursor purging step constitute the organic precursor sub-cycle.

[0183] Subsequently, with the gas outlet closed, the Zn precursor DEZ (diethylzinc) is supplied as an inorganic precursor to the organic precursor layer through the gas inlet under carrier gas-free conditions until the chamber pressure reaches 1 Torr (inorganic precursor supply step). Afterward, the gas inlet is also closed, maintaining the chamber pressure at 1 Torr, and the Zn precursor is allowed to react on the surface of the organic precursor layer for 1 second (inorganic precursor exposure step). Then, with both the gas inlet and outlet open, argon gas (purge gas) is supplied through the gas inlet for 200 seconds to purge reaction byproducts and residual reaction gases (inorganic precursor purging step). The inorganic precursor supply step, inorganic precursor exposure step, and inorganic precursor purging step constitute the inorganic precursor sub-cycle.

[0184] A unit cycle consisting of an inorganic precursor sub-cycle and an organic precursor sub-cycle is executed 33 times to form a multilayer molecular film photoresist with a thickness of approximately 20 nm.

[0185] Manufacturing Example 2: Photoresist Manufacturing Example 2

[0186] The same organic precursor sub-cycle as in Manufacturing Example 1 was performed. Then, with the gas outlet closed, the inorganic precursor Hf precursor (TDMA)Hf (tetra(dimethylamino)hafnium) was supplied to the organic precursor layer through the gas inlet under carrier gas-free conditions until the chamber pressure reached 750 mTorr (inorganic precursor supply step). Subsequently, the gas inlet was closed, and the chamber pressure was maintained at 750 mTorr, allowing the Hf precursor to react on the surface of the organic precursor layer for 1 second (inorganic precursor exposure step). Then, with both the gas inlet and gas outlet open, argon gas was supplied through the gas inlet as a purge gas for 300 seconds to purge reaction byproducts and residual reaction gases (inorganic precursor purging step). The inorganic precursor supply step, the inorganic precursor exposure step, and the inorganic precursor purging step constitute the inorganic precursor sub-cycle.

[0187] A unit cycle consisting of an inorganic precursor sub-cycle and an organic precursor sub-cycle is executed 31 times to form a multilayer molecular film photoresist with a thickness of approximately 20 nm.

[0188] Manufacturing Example 3: Photoresist Manufacturing Example 3

[0189] The same organic precursor sub-cycle as in Manufacturing Example 1 was performed. Then, with the gas outlet closed, the inorganic precursor Ti precursor (TDMA)Ti (tetra(dimethylamino)titanium) was supplied to the organic precursor layer through the gas inlet under carrier gas-free conditions until the chamber pressure reached 1 Torr (inorganic precursor supply step). Then, with the gas inlet also closed and the chamber pressure maintained at 1 Torr, the Ti precursor was reacted on the surface of the organic precursor layer for 1 second (inorganic precursor exposure step). Afterwards, with both the gas inlet and outlet open, argon gas (purge gas) was supplied through the gas inlet for 300 seconds to purge reaction byproducts and residual reaction gases (inorganic precursor purging step). The inorganic precursor supply step, inorganic precursor exposure step, and inorganic precursor purging step constitute the inorganic precursor sub-cycle.

[0190] A unit cycle consisting of an inorganic precursor sub-cycle and an organic precursor sub-cycle is executed 42 times to form a multilayer molecular film photoresist with a thickness of approximately 20 nm.

[0191] Figure 9The graphs show the film growth rate as a function of the supply time of each precursor during the fabrication of photoresist according to Manufacturing Example 1. The left graph shows the film growth rate as a function of the DEZ supply time when the DMP supply time is fixed at 5 seconds. The right graph shows the film growth rate as a function of the DMP supply time when the DEZ supply time is fixed at 2 seconds.

[0192] refer to Figure 9 The membrane growth rate reached saturation approximately after 2 seconds of DEZ supply and approximately 5 seconds of DMP supply. Furthermore, by setting the DEZ supply time to 2 seconds and the DMP supply time to 5 seconds, approximately [a certain percentage] of [something] was achieved. / Cyclic membrane growth rate.

[0193] Figure 10 The graph showing the change in film thickness of the photoresist according to manufacturing example 1 with the number of cycles and the AFM image of the surface are shown.

[0194] refer to Figure 10 According to the photoresist in manufacturing example 1, it exhibits... / Cyclic film formation rate, and achieved a surface with small surface roughness.

[0195] Figure 11 SEM images of the photoresist obtained in Manufacturing Example 1 after patterning are shown. Specifically, the photoresist obtained in Manufacturing Example 1 was patterned at 100 kV, 500 pA, and 1500 μC / cm. 2 The photoresist was then exposed to an electron beam under specific conditions. Subsequently, the photoresist was immersed in a 2 wt% TMAH (tetramethylammonium hydroxide) H2O solution for 2 minutes, followed by immersion in H2O for 10 seconds for development.

[0196] refer to Figure 11 A pattern with a half-pitch linewidth of 1 μm was clearly formed. The pattern was formed in the exposed area, and the photoresist in this example can be defined as a negative photoresist.

[0197] Figure 12 It is shown Figure 11 A schematic diagram of the cross-linking of the photoresist during the exposure process.

[0198] refer to Figure 12 It can be assumed that within the irradiation region, the unreacted functional groups (i.e., ethyl groups) of the inorganic monomer bonded to the organic monomer react with the unreacted functional groups (i.e., thiol groups) of the adjacent organic monomer to form Zn-SC bonds. Furthermore, it can be considered that the Zn in the inorganic monomer coordinates with the O and / or S in the adjacent organic monomer layer.

[0199] It is speculated that these Zn-SC bonds and coordinate bonds cause the exposed areas to remain undeveloped, thus forming patterns.

[0200] Figure 13 A graph showing the electron beam sensitivity of the photoresist obtained in Manufacturing Example 1. Specifically, the photoresist obtained in the manufacturing example was subjected to an electron beam sensitivity of 5 mJ / cm. 2 Up to 200mJ / cm 2 Expose to EUV within the dose range, then immerse in 2 wt% TMAH (tetramethylammonium hydroxide) H2O solution for 2 minutes, followed by immersion in H2O for 10 seconds for development.

[0201] refer to Figure 13 In this experiment, the normalized thickness of the negative photoresist, when maintained at the thickness immediately after deposition after development, is expressed as 1. The multilayer molecular film photoresist according to the manufacturing example has a thickness of approximately 150 mJ / cm². 2 It exhibits a normalized thickness of 1, demonstrating excellent sensitivity.

[0202] Figure 14 To illustrate the EUV irradiation pattern and dosage conditions, Figure 15 To manufacture the photoresist according to Example 1, using... Figure 14 An optical photograph of the photoresist pattern obtained after EUV pattern irradiation. Specifically, the photoresist according to the manufacturing example is exposed to an environment such as... Figure 14 The EUV pattern shown was then immersed in a 2 wt% TMAH (tetramethylammonium hydroxide) H2O solution for 2 minutes, followed by immersion in H2O for 10 seconds for development.

[0203] refer to Figure 14 and Figure 15 According to the manufacturing example, the photoresist immediately after deposition exhibits a thickness of approximately 20 nm, when a dosage of approximately 15 mJ / cm is used. 2 After exposure to or higher EUV and development, a thickness of approximately 10 nm or higher is observed. This indicates that the EUV sensitivity of the photoresist according to Manufacturing Example 1 is 15 mJ / cm. 2 .

[0204] Figure 16 To show the graph of the change in film thickness of the photoresist according to manufacturing example 2 with the number of cycles and the AFM image of the surface.

[0205] refer to Figure 16 According to the photoresist in manufacturing example 2, it exhibits... / Cycle film growth rate, and produce a surface with moderate surface roughness.

[0206] Figure 17 To show the graph of the change in film thickness of the photoresist according to manufacturing example 3 with the number of cycles and the AFM image of the surface.

[0207] refer to Figure 17 According to the photoresist in manufacturing example 3, it exhibits... / Cycle film growth rate, and produce a surface with moderate surface roughness.

[0208] Although exemplary embodiments of the present invention have been described above, those skilled in the art will understand that various changes, substitutions and modifications can be made therein without departing from the spirit and scope of the invention as defined by the following claims.

Claims

1. A multilayer molecular film photoresist, comprising: Multiple molecular lines extending upwards from the substrate and arranged laterally, each containing linearly linked monomers represented by the following chemical formula 1: [Chemical Formula 1] In the chemical formula 1, one of the * is a bond connected to a functional group in the monomer below, and the other of the * is a bond connected to a functional group in the monomer above, OM is an organic monomer, MM is a main inorganic monomer containing a metal atom, m is 1 to 2, n is 1 to 2, and l is 1 to 1000. A lateral inorganic monomer, located between the molecular lines and bonded to the lateral side of the organic monomer (OM) in one of the molecular lines, comprising a metal atom; and Cross-linked functional groups bonded to the side of the organic monomer (OM) in another molecular line.

2. The multilayer molecular film photoresist according to claim 1, wherein, There are van der Waals interactions between the organic monomers within the laterally adjacent molecular lines.

3. The multilayer molecular film photoresist according to claim 1, wherein, The main inorganic monomer is represented by the following chemical formula 2: [Chemical Formula 2] In chemical formula 2, one of the * represents a bond connected to a functional group in the lower monomer, and the other of the * represents a bond connected to a functional group in the upper monomer. X a It is O, S, Se, NR (R is H or CH3) or PR (R is H or CH3). M 0 It is the metal atom, and M 0 is Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W or Si, Z1 and Z2 are independently of each other a direct bond, a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched oxoalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylsilylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylseleno group having 1 to 20 carbon atoms, or a substituted or unsubstituted straight-chain or branched alkylphosphin group having 1 to 20 carbon atoms, and L a With L b Independently comprising a halogen group, a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkylthio group, a C1 to C5 alkylselenyl group, a C1 to C5 alkylamino group, a C1 to C5 alkylphosphinyl group, an acetate group, or an aryloxy group, and The sum of na and nb is an integer between 0 and 4.

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

5. The multilayer molecular film photoresist according to claim 1, wherein, The inorganic monomer on the side is represented by the following chemical formula 3: [Chemical Formula 3] In chemical formula 3, * represents the bond connected to the organic monomer. X c For O, S, Se, NR (R is H or CH3) or PR (R is H or CH3), M 0 It is the metal atom, and M 0 is Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W or Si, Z1 and Z2 are independently of each other a direct bond, a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched oxoalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylsilylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylseleno group having 1 to 20 carbon atoms, or a substituted or unsubstituted straight-chain or branched alkylphosphin group having 1 to 20 carbon atoms, and L a With L b Independently, they are halogen groups, C1 to C5 alkyl groups, C1 to C5 alkylsilylamino groups, C1 to C5 alkoxy groups, C1 to C5 alkylthio groups, C1 to C5 alkylselenyl groups, C1 to C5 alkylamino groups, C1 to C5 alkylphosphinyl groups, acetate groups, or aryloxy groups. The sum of na and nb is an integer between 0 and 4, and R b2 It is a halogen group (e.g., Cl, Br or I), C1 to C5 alkyl, C1 to C5 alkylsilylamino, C1 to C5 alkoxy, C1 to C5 alkylthio, C1 to C5 alkylselenyl, C1 to C5 alkylamino or C1 to C5 alkylphosphinyl.

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

7. The multilayer molecular film photoresist according to claim 1, in, The crosslinking functional group is *-Z5X. c R a3 , Wherein, * represents the bond connected to the organic monomer, Z5 is a direct bond or a substituted or unsubstituted straight-chain or branched C1 to C5 alkylene group, specifically a C1 to C3 alkylene group, X c For O, S, Se, NR (R is H or CH3) or PR (R is H or CH3), and R a3 It is hydrogen or C1 to C2 alkyl.

8. The multilayer molecular film photoresist according to claim 1, in, The organic monomer is represented by the following chemical formula 4: [Chemical Formula 4] *-X b -Z3-MR-Z4-* In the chemical formula 4, one of the * is a bond connected to a functional group in the lower monomer, and the other of the * is a bond connected to a functional group in the upper monomer; X b For O, S, Se, NR (R is H or CH3) or PR (R is H or CH3); Z3 and Z4 are independently C1 to C5 alkylene groups, either directly bonded, straight-chain, or branched. MR is a straight-chain structure having 2 to 7 carbons or a non-aromatic or aromatic ring having 3 to 18 carbons; and The inorganic monomer or the cross-linked functional group is bonded to the host (MR).

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

10. A multilayer molecular film photoresist, comprising: Multiple molecular lines extending upwards from the substrate and arranged laterally, each molecular line comprising linearly connected monomers, wherein each monomer comprises a plurality of host inorganic monomers containing metal atoms and organic monomers connected between at least a portion of the host inorganic monomers; and The inorganic monomer located between the molecular lines is bonded to the side of the organic monomer and contains metal atoms.

11. The multilayer molecular film photoresist according to claim 10, wherein, The main inorganic monomer and the organic monomer located within the molecular line are connected by a bond selected from -O-, -S-, -Se-, -NR- (R is H or CH3) and -PR- (R is H or CH3) contained in any of these monomers.

12. The multilayer molecular film photoresist according to claim 10, wherein, The organic monomer and the inorganic monomer are linked by a bond selected from -O-, -S-, -Se-, -NR- (R is H or CH3) and -PR- (R is H or CH3) contained in any of these monomers.

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

14. The multilayer molecular film photoresist according to claim 10, wherein, There are van der Waals interactions between the organic monomers within the laterally adjacent molecular lines in the molecular lines.

15. The multilayer molecular film photoresist according to claim 10, wherein, Each of the molecular lines is formed by the alternating stacking of the main inorganic monomer and the organic monomer.

16. The multilayer molecular film photoresist according to claim 10, wherein the multilayer molecular film photoresist is a photoresist for EUV.

17. A method for manufacturing a photoresist pattern, comprising: A multilayer molecular film photoresist is provided, the multilayer molecular film photoresist comprising multiple molecular lines extending upward from a substrate and arranged laterally, each molecular line comprising linearly connected monomers represented by the following chemical formula 1: [Chemical Formula 1] In chemical formula 1, one of the asterisks represents a bond connected to a functional group in the monomer below, and the other of the asterisks represents a bond connected to a functional group in the monomer above; OM represents an organic monomer; MM represents a main inorganic monomer containing a metal atom; m is 1 to 2, n is 1 to 2, and l is 1 to 1000. An inorganic monomer located between the molecular lines, bonded to the side of the organic monomer (OM) in one of the molecular lines and containing a metal atom; and a cross-linking functional group bonded to the side of the organic monomer (OM) in the other molecular line; A portion of the multilayer molecular film photoresist is irradiated with Ebeam or EUV radiation to crosslink the side inorganic monomer molecules with the crosslinkable functional groups; as well as The unexposed portions of the multilayer molecular film photoresist are developed and removed.

18. A method for manufacturing a photoresist pattern, comprising: The substrate is loaded into a chamber with a gas inlet and a gas outlet; Performing an organic precursor sub-cycle includes supplying an organic precursor of Formula 5 into the chamber with the gas outlet closed, allowing the organic precursor to react on the substrate, and then purging any residual reaction gas in the chamber. Performing an inorganic precursor sub-cycle includes supplying an inorganic precursor of chemical formula 6 into the chamber with the gas outlet closed, causing the inorganic precursor to react on the organic precursor, and then purging any residual reaction gas in the chamber. Multiple unit cycles, including the organic precursor sub-cycle and the inorganic precursor sub-cycle, are executed to form a multilayer molecular film photoresist. A portion of the multilayer molecular film photoresist is irradiated with Ebeam or EUV radiation. Develop the areas of the multilayer molecular film photoresist that were not exposed to the radiation: [Chemical Formula 5] In the chemical formula 5, R a1 R a2 and R a3 Each of the above is independently hydrogen or C1 to C2 alkyl, X a X b and X c Each of the following is independently O, S, Se, NR (R is H or CH3) or PR (R is H or CH3); Z3, Z4 and Z5 are independently direct-linked or substituted or unsubstituted straight-chain or branched C1 to C3 alkylene groups; MR is a straight-chain group having 2 to 7 carbons or a non-aromatic or aromatic ring group having 3 to 18 carbons; x is 1 or 2. [Chemical Formula 6] In the chemical formula 6, R b1 With R b2 Independently, they are halogen groups, C1 to C5 alkyl groups, C1 to C5 alkylsilylamino groups, C1 to C5 alkoxy groups, C1 to C5 alkylthio groups, C1 to C5 alkylselenyl groups, C1 to C5 alkylamino groups, or C1 to C5 alkylphosphinyl groups. M 0 is Sn, Sb, Te, Bi, Zr, Al, Hf, Zn, In, Al, Ti, Cu, W or Si, Z1 and Z2 are independently of each other a direct bond, a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched oxoalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylsilylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted straight-chain or branched alkylseleno group having 1 to 20 carbon atoms, or a substituted or unsubstituted straight-chain or branched alkylphosphin group having 1 to 20 carbon atoms, and L a With L b Independently comprising a halogen group, a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, a C1 to C5 alkoxy group, a C1 to C5 alkylthio group, a C1 to C5 alkylselenyl group, a C1 to C5 alkylamino group, a C1 to C5 alkylphosphinyl group, an acetate group, or an aryloxy group, and The sum of na and nb is an integer between 0 and 4.

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