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

Abstract

To provide a photoresist having excellent photon absorptivity and low line edge roughness.SOLUTION: A multilayer molecular film photoresist, comprising: a plurality of molecular beams extending in an upper direction of a substrate and arranged in a horizontal direction, wherein each of the molecular beams includes a plurality of inorganic monomolecules and organic monomolecules interposed between at least some of the inorganic monomolecules, the inorganic monomolecules and the organic monomolecules being connected to each other by bonding.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Photoresists have been continuously studied, especially liquid photosensitive liquids. The most actively researched method is to spin coat and deposit the film onto a substrate after manufacturing. Traditional photoresists include polymer resins, such as PAG (Photo-Acid Gen Chemical amplification containing a base (quencher) and a base (amplifier). Photoresist (Chemically Amplified Resist; CAR) is mainly used.

[0003] Recently, the semiconductor industry has been focusing on extreme ultraviolet (Ex) light, which can form ultra-fine patterns of less than 10 nm. EUV exposure technology using treme ultraviolet (EUV) light source (Photo o Lithography) has been introduced.

[0004] However, EUV is 1 / 14th the wavelength of 193nm DUV (deep UV). Having a low photon density reduces stochastic failure ), specifically, chemical stochastic failure For example, in the case of CAR, low photon density can induce P The probability of AG reacting is low, so shot noise may occur. In this case, the size of the polymer resin particles is large, at 4 nm or more, and the line edge roughness is relatively large. It is known to have the drawback of line edge roughness. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, the problem to be solved by the present invention is to provide a method for manufacturing a semiconductor device having excellent photon absorption and low line edge roughness. The object of the present invention is to provide a photoresist having a low

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

[0007] According to one embodiment of the present invention, there is provided a multilayer molecular film photoresist. The photoresist is provided with a number of molecular beams arranged laterally and extending upward from the substrate. Each molecular beam is composed of a large number of inorganic monomolecules and at least some of the inorganic monomolecules. The organic molecules are connected by bonds between the molecules.

[0008] The van der Waals gap between the organic monomolecules in the laterally adjacent molecular beams among the molecular beams The van der Waals interactions can be π-π bonds. It's possible.

[0009] Each of the molecular beams is formed by alternately stacking and bonding the inorganic monomolecules and the organic monomolecules. It is also possible.

[0010] The inorganic monomolecules provided on the molecular beam are arranged in the same horizontal direction to form an inorganic monomolecular layer. The inorganic monomolecules provided on the molecular beam are arranged in the same horizontal direction to form an organic monomolecular layer. It can be achieved.

[0011] The multilayer molecular film photoresist includes a light-absorbing layer including a light-absorbing inorganic monomer, a photo-reactive inorganic monomer, and a a photoreactive layer comprising an inorganic monolayer and an etching-resistant layer comprising an etching-resistant inorganic monolayer; The light-absorbing inorganic monolayer may have at least one layer. The metal element in the light-absorbing inorganic monolayer may be: The photoreactive inorganic monolayer may be Sn, Sb, Te, or Bi. The etching-resistant inorganic monolayer may have a metal element selected from the group consisting of Zn, In, and Al. It can have a metallic element of Al, Ti, W, Zn, or Cu.

[0012] According to one embodiment of the present invention, there is provided another example of a multilayer molecular film photoresist. The layer molecular film photoresist extends upward from the substrate and is arranged in a large number of layers in the horizontal direction. Each of the molecular beams has a layer represented by the following chemical formula 1:

[0013] [ka] In the above formula 1, 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, M is an inorganic monomolecule containing a metal element, and O is It is an organic monomolecular compound, m is 1 to 2, n is 1 to 2, and l is 1 to 1000. The organic monomer may be represented by the following Chemical Formula 3:

[0014] [ka] In the above Chemical Formula 3, one of the * is a bond to a functional group in the lower layer, and the remaining one The first is bonding with functional groups in the upper layer, and the second is bonding with functional groups in the upper layer. bis O, S, Se, NR (R is H or C H3) or PR (R is H or CH3), and MR is a substituted or unsubstituted aromatic ring. or a C1 to C18 substituted or unsubstituted, linear or branched alkylene group. When MR is the aromatic ring, Z3 and Z4 are each independently a bond or C1-C5 substituted or unsubstituted, linear or branched alkylene group, and MR is When the alkylene group is mentioned above, Z3 and Z4 are bonds.

[0015] In the formula 1, M is a light-absorbing inorganic monolayer containing a metal element having a d orbital. , Zr, Al, Hf, Zn, or In-containing photoreactive inorganic monomolecules, or Al, Ti, It can be an etch-resistant inorganic monolayer containing Cu, W, or Zn.

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

[0017] [ka] In the above Chemical Formula 1A, one of the *'s is a bond to a functional group in the lower layer, and the remaining One is bonding with a functional group in the upper layer, where M1 contains a metal element with a d orbital. O1 is a light-absorbing inorganic monolayer, O2 is an organic monolayer, m1 is 1 to 2, and n1 is , 1 to 2, and l1 can be 1 to 1000.

[0018] Each of the molecular beams is formed by depositing a layer represented by the following Chemical Formula 1B on or under the layer represented by the Chemical Formula 1A. It can be equipped with:

[0019] [ka] In Chemical Formula 1B, one of the *'s is a bond to a functional group in the lower layer, and the remaining One is bonding with a functional group in the top layer, where M2 is Zr, Al, Hf, Zn, or I. n is a photoreactive inorganic monolayer, O2 is an organic monolayer, and m2 is 1 to 2; n2 can be 1 to 2, and l2 can be 1 to 1000.

[0020] Each of the molecular beams is formed by depositing a layer represented by the following Chemical Formula 1C on or under the layer represented by the Chemical Formula 1A. It can be equipped with:

[0021] [ka] In Chemical Formula 1C, one of the *'s is a bond to a functional group in the lower layer, and the remaining One is bonding with functional groups in the upper layer, M3 includes Al, Ti, Cu, W, and Zn. is an etching-resistant inorganic monolayer, O3 is an organic monolayer, m3 is 1 to 2, and n 3 can be 1 to 2, and l3 can be 1 to 1000.

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

[0023] According to another embodiment of the present invention, a multilayer molecular film photoresist deposition apparatus is provided. The multilayer molecular film photoresist deposition equipment is configured to have a plurality of layers extending in the direction of the top of the substrate and a plurality of layers extending in the direction of the side of the substrate. Each molecular beam has a layer represented by the following chemical formula 1: A multilayer molecular film photoresist is prepared, and the layer represented by Chemical Formula 1 is formed by disposing a metal monolayer on a substrate. The method is carried out many times using a cycle including a step of forming a layer and a step of forming an organic molecular layer. do.

[0024] [ka] In the above Chemical Formula 1, one of the * is a bond to a functional group in the lower layer, and the remaining * is a bond to a functional group in the lower layer. The first is a bond with a functional group in the upper layer, M is an inorganic monomolecular molecule containing a metal element, and O is , an organic monomolecular compound, m is 1 to 2, n is 1 to 2, and l is 1 to 1000. The organic monomer may be represented by the following Chemical Formula 3:

[0025] [ka] In the above Chemical Formula 3, one of the * is a bond to a functional group in the lower layer, and the remaining one The first is bonding with functional groups in the upper layer, and the second is bonding with functional groups in the upper layer. b is O, S, Se, NR (R is H or C H3) or PR (R is H or CH3), and MR is a substituted or unsubstituted aromatic ring. or a C1 to C18 substituted or unsubstituted, linear or branched alkylene group. When MR is the aromatic ring, Z3 and Z4 are each independently a bond or C1-C5 substituted or unsubstituted, linear or branched alkylene group, and MR is When the alkylene group is mentioned above, Z3 and Z4 are bonds.

[0026] In the formula 1, M is a light-absorbing inorganic monolayer containing a metal element having a d orbital. , Zr, Al, Hf, Zn, or In-containing photoreactive inorganic monomolecules, or Al, Ti, It can be an etch-resistant inorganic monolayer containing Cu, W, or Zn. [Effects of the Invention]

[0027] The multilayer molecular film photoresist according to one embodiment of the present invention is particle-free during exposure and development. By separating the molecular beams, the line edge roughness (Lin The edge roughness (LER) can be as low as 1.2 nm or less. Moreover, the resolution can be significantly improved to 6 nm or less.

[0028] In addition, the multilayer molecular film photoresist has, in one example, a light absorption rate of EUV Equipped with very tall inorganic atoms, specifically metal atoms with 4d or 5d orbitals It contains light-absorbing inorganic single molecules and exhibits stochastic defects (Stochas Low tic failure and high light sensitivity (ex. 10 mJ / cm 2 ) can be shown can. [Brief explanation of the drawings]

[0029] [Figure 1] FIG. 1 is a schematic diagram showing a multilayer molecular film photoresist having a vertical molecular beam structure according to one embodiment of the present invention. [Figure 2] FIG. 2 is a schematic view showing another example of a light absorption layer in a multilayer molecular film photoresist having a vertical molecular beam structure according to an embodiment of the present invention. [Figure 3] FIG. 3 is a schematic diagram illustrating the steps of a photolithography method according to one embodiment of the present invention. [Figure 4] FIG. 4 is a schematic diagram illustrating the steps of a photolithography method according to one embodiment of the present invention. [Figure 5] FIG. 5 is a schematic diagram illustrating the steps of a photolithography method according to one embodiment of the present invention. [Figure 6] FIG. 6 is a schematic diagram illustrating the steps of a photolithography method according to one embodiment of the present invention. [Figure 7] FIG. 7 is a schematic diagram illustrating the steps of a photolithography method according to one embodiment of the present invention. [Figure 8]FIG. 8 shows a unit cycle configuration for forming an inorganic molecular layer. [Figure 9] FIG. 9 is an SEM image taken after patterning the vertically designed inorganic multilayer molecular photoresist formed with reference to FIG. [Figure 10] FIG. 10 shows a unit cycle configuration for forming a multilayer molecular film photoresist having a vertical molecular beam structure. [Figure 11a] FIG. 11a is an SEM image taken after patterning the photoresist formed using the method described with reference to FIG. [Figure 11b] FIG. 11b is an SEM image taken after patterning the photoresist formed using the method described with reference to FIG. [Figure 11c] FIG. 11c is an SEM image taken after patterning the photoresist formed using the method described with reference to FIG. [Figure 12] FIG. 12 is a graph showing the electron beam sensitivity of a photoresist formed using the method described with reference to FIG. [Figure 13a] FIG. 13a is a schematic diagram showing the form and dose conditions for EUV irradiation. [Figure 13b] FIG. 13b is an optical photograph of the photoresist pattern obtained when EUV, as shown in FIG. 13a, is irradiated onto a photoresist using a Hf precursor formed using the method described with reference to FIG. 10. [Figure 14a] FIG. 14a is an atomic force microscopy (AFM) image obtained after electron beam exposure and development of a photoresist using a Zn precursor formed using the method described with reference to FIG. [Figure 14b] FIG. 14b is an atomic force microscopy (AFM) image obtained after electron beam exposure and development of the PMMA photoresist. DETAILED DESCRIPTION OF THE INVENTION

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

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

[0032] In this specification, a single molecule means a molecule that is not a polymer, and an example of such a molecule is a small molecule (sm all molecule), specifically, 100 atoms or less, specifically, 3 atoms It means 0 or fewer molecules.

[0033] As used herein, molecules or functional groups are "linked by a bond" when they are directly They are directly linked, or indirectly linked by other molecules or functional groups placed between them. It can also mean that it is connected to

[0034] In the present specification, when it is stated that "the number of carbon atoms (C)X to the number of carbon atoms (C)Y" is used, the number of carbon atoms X and the carbon number Y. For example, if C1 to C10 are listed, it should be interpreted as C1, C2, C3, C4, C5, C6, C7, C8, C9, and C10 are all considered to be listed. should be.

[0035] In this specification, when "X to Y" is stated, it corresponds to all integers between X and Y. For example, if you write 1 to 10, , 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 are all considered to be listed. It should be.

[0036] FIG. 1 shows a multilayer molecular film photoresist having a vertical molecular beam structure according to one embodiment of the present invention. FIG.

[0037] Referring to Figure 1, a substrate 10 can be provided. The substrate can be a semiconductor substrate, a glass substrate, or any suitable material. The substrate may be a bare substrate such as a glass substrate or a flexible substrate. The flexible substrate may be a polymer substrate. , diodes, solar cells, optical elements, biosensors, nanoelectromechanical systems (NEMS), Microelectromechanical systems (MEMS), nanodevices, or chemical sensors, etc. The element may be an organic light emitting diode. The organic electronic device may be an organic electronic device such as an organic solar cell. The plate 10 is the bare substrate or the bare substrate on which the elements are formed. It may also be the case.

[0038] The etching target layer 20 may be formed on the substrate 10. 0 is the etching mask used after forming the photoresist pattern. It is a layer that is etched to form a pattern and is made of various materials used in semiconductor manufacturing. For example, the layer to be etched 20 may be a metal film, a semiconductor film, an insulating film, Alternatively, it may be a composite film containing any one of these. The material is aluminum, tungsten, titanium, or any of these. The semiconductor film may be a silicon film, for example, a single crystal silicon film. Silicon, polysilicon, amorphous silicon film, or any one of these The insulating film may be an inorganic insulating film such as a silicon oxide film or a silicon nitride film. film; organic insulating film such as amorphous carbon film; or composite film containing any one of these In one example, the layer to be etched 20 is the bare substrate. That's fine.

[0039] The surface functional groups of the layer to be etched 20, for example, hydroxyl groups, thiol groups, amino groups, or a phenyl group, or a phosphine group, The surface may be treated to have this.

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

[0041] The multilayer molecular film photoresist 30 is made up of inorganic monomolecules (M1, M2, or M 3) has a large number of molecular beams ML connected directly or indirectly by bonds in the horizontal direction. In this case, the indirect connection means that the inorganic monomolecules M1, M2, or or M3, other monomolecules, such as the organic monomolecules O1, O2, or O3 described below, The bond may be a covalent bond or a coordinate bond. In one example, the molecular beam ML is directed upward, for example, perpendicularly to the substrate 10. The lateral direction may be substantially parallel to the surface of the substrate 10. It's possible.

[0042] In this embodiment, the multilayer molecular film photoresist 30 is formed by atomic layer deposition (ALD). Layer Deposition or Molecular Layer Deposition Since it is formed using layer deposition, it is a multilayer molecular film photoresist. Almost all molecular beams ML in 30 can have substantially the same layer structure. As a result, the molecular beam ML in the multilayer molecular film photoresist 30 is formed in the same lateral direction as the same inorganic monolayer. In other words, the inorganic monolayer provided on the molecular beam can have the same organic monolayer. The molecules are arranged in the same horizontal direction to form an inorganic monolayer, and the organic monolayers provided on the molecular beam The molecules can be laterally arranged in the same order to form an organic monolayer.

[0043] The multilayer molecular film photoresist 30 may be an organic / inorganic multilayer molecular film photoresist. Specifically, the multilayer molecular film photoresist 30 is formed by removing a part of the atomic particles contained in each molecular beam ML. The organic molecules O1, O2, and O3 are bonded between the inorganic molecules M1, M2, and M3. In this case, the multilayer molecular film photoresist 30 is made of organic monomolecules O1, O2, O 3 and inorganic single molecules M1, M2, and M3 are connected by bonds. The organic monomolecules O1, O2, and O3 in the adjacent molecular beams ML are In this case, the van der Waals interactions VI may be present between the two molecules. The VI interaction stabilizes laterally adjacent molecular beams ML, resulting in a high aspect ratio. Even in such a case, it can prevent the pattern from being destroyed. The rus interaction can be, in one example, a π-π bond between aromatic groups.

[0044] The multilayer molecular film photoresist 30 has a layer structure represented by the following chemical formula 1: can be done.

[0045] [ka] In the above formula 1, one of the * represents a functional group in the lower layer or a functional group in the lower monolayer. The remaining one may be a bond to a functional group in the upper layer or a functional group in the upper monolayer. In this case, the bond may be, for example, a covalent bond. M may be an organic single molecule. Specifically, OM is an organic single molecule represented by the following formula 3: In the above formula 1, m may be 0 to 10, and n may be 1 to 2. 10, and l is 1 to 10,000, specifically 20 to 1,000, more specifically Typically, m may be 25 to 100. Specifically, m may be 1 to 2, for example, m may be 1. n may also be 1 to 2, for example, n may be 1.

[0046] The MM can be an inorganic monomolecule containing a metal element, specifically an organometallic monomolecule. For example, light-absorbing inorganic single molecules containing metal elements with d orbitals, such as Zr, Al, and H Photoreactive inorganic monomolecules containing f, Zn, or In, or Al, Ti, Cu, W, or The d orbital, specifically, the 4d orbital, may be an etching-resistant inorganic monolayer containing Zn. Examples of metallic elements with 5d or 5d orbitals include Sn, Sb, Te, and Bi. Here, the classification of inorganic monomolecules refers to the main function, and all the described The inorganic monomolecules can absorb light and undergo photoreaction. The MM can be represented by the following chemical formula 2, specifically: The organic metal monolayer may be represented by the following formula 2A, 2B, or 2B.

[0047] [ka] In the above formula 2, one of the * represents a functional group in the lower layer or a functional group in the lower monolayer. The remaining one may be a bond to a functional group in the upper layer or a functional group in the upper monolayer. In this case, the bond may be, for example, a covalent bond. 1 and Z2 are, independently of each other, a bond, a C1-C20 substituted or unsubstituted linear or Branched alkylene groups, C1-C20 substituted or unsubstituted linear or branched alkylene groups oxide, C1-C20 substituted or unsubstituted linear or branched alkyleneamino, C1- C20 substituted or unsubstituted linear or branched alkylenesilylamino, C1-C20 Substituted or unsubstituted linear or branched alkylene thio, C1-C20 substituted or unsubstituted or a C1-C20 substituted or unsubstituted linear or branched alkylene seleno or branched alkylenephosphino. M 0 is a light-absorbing metal with d orbitals atoms, photoreactive metal atoms such as Zr, Al, Hf, Zn, or In, or Al, Ti The d orbital, in particular, may be an etching-resistant metal atom such as Cu, W, or Zn. Specifically, metallic elements with 4d or 5d orbitals include, for example, Sn, Sb, and T. e, or Bi. a is O, S, Se, NR (R is H or CH3) or It can be PR (R is H or CH3).

[0048] L a and L b is M 0 The number of ligands bound to na and nb The sum of these is M 0 The coordination number can be determined by the resulting coordinate system. For example, na and n The sum of b can be an integer from 1 to 4. a and L b are halogen groups (ex Cl, Br, or I), C1-C5 alkyl groups, C1-C5 alkylsilylamino groups a C1-C5 alkoxy group, a C1-C5 alkylthio group, a C1-C5 alkyl Seleno group, C1-C5 alkylamino group, or C1-C5 alkylphosphine group Here, the C1-C5 alkyl group may be a substituted or unsubstituted, linear or In addition, in the above Chemical Formula 2, na and / or nb may be a branched alkyl group. If 2 or more, L a and / or L b Select from the above examples regardless of each other. In one example, if the sum of na and nb is 2 or more, L a and L b Two of them are , and these are attached M 0 to form a heterocyclyl or heteroaryl Z1, Z2, L a , or L b and M 0 Each bond between It may be a bond or a coordinate bond.

[0049] In one example, the multilayer molecular film photoresist 30 is made of the inorganic monomolecules, specifically, The light absorption layer FL1, the light reaction layer FL2, and the anti-reflection layer FL3 are classified according to the type of organometallic monomolecules. At least one etching layer FL3 may be provided. The components refer to the main functions, and all layers are responsible for the generation of secondary electrons by light absorption and the As an example, the multilayer molecular film photoresist 30 may be The light-absorbing layer FL1, the photo-reactive layer FL2, and the light-reactive layer FL3 may be included. The lamination order of the etching-resistant layer FL3 depends on the type of the etching target layer 20 and / or the thickness of the etching target layer 20. It can be changed depending on the type of pattern to be formed through photolithography. .

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

[0051] [ka] In the above formula 1A, one of the * represents a functional group in the lower layer or a lower monomolecular inner group. The other bond may be to a functional group in the upper layer or to a functional group in the upper monolayer. In this case, the bond may be, for example, a covalent bond. M1 is a light-absorbing inorganic monolayer, for example, a d-orbital, specifically, a 4d or Metallic elements with 5d orbitals, for example, Sn, Sb, Te, or Bi O1 may be an organic metal monolayer, and m1 may be an organic monolayer. where n1 may be 1 to 10, and l1 may be 1 to 1000. Specifically, m1 may be 1 or 2, for example, m1 may be 1. n1 may also be 1 or 2, for example, For example, n1 may be 1. The light-absorbing inorganic monolayer M1 may be represented by the following Formula 2A: In the above-mentioned Chemical Formula 1A, n1 is 2 or more. When l1 is 2 or more, the light-absorbing inorganic monomolecules M1 in each layer may be the same or different. That's fine.

[0052] [ka] In the above formula 2A, one of the * represents a functional group in the lower layer or a lower monomolecular inner group. The other bond may be to a functional group in the upper layer or to a functional group in the upper monolayer. In this case, the bond may be, for example, a covalent bond. Z1 and Z2 are independently a bond, a C1-C20 substituted or unsubstituted linear or is a branched alkylene group, a C1-C20 substituted or unsubstituted linear or branched alkylene oxide, C1-C20 substituted or unsubstituted linear or branched alkyleneamino, C1 C1-C20 substituted or unsubstituted linear or branched alkylenesilylamino substituted or unsubstituted linear or branched alkylene thio, C1-C20 substituted or unsubstituted Substituted linear or branched alkyleneseleno, or C1-C20 substituted or unsubstituted linear Or it can be a branched alkylenephosphino. a radiation, specifically EUV or or inorganic atoms with good E-beam absorption, e.g., d orbital, e.g., 4 The metal atom may be a metal atom having a d or 5d orbital. X can be n, Bi, Sb, or Te. a is O, S, Se, NR (R is H or C H3) or PR (R is H or CH3).

[0053] In the formula 2A, L1 and L2 are each M a a ligand bound to the ligand, The sum of n1 and n2, which are the numbers of nodes, is M aThe coordination number is determined by For example, the sum of n1 and n2 can be an integer between 1 and 4. L1 and L2 are mutually related. Regardless of the above, halogen groups (e.g., Cl, Br, or I), C1-C5 alkyl groups, C1-C5 alkyl groups, C5 alkylsilylamino group, C1-C5 alkoxy group, C1-C5 alkylthio group alkylthio group, C1-C5 alkylseleno group eleno group), C1-C5 alkylamino oup), or C1-C5 alkylphosphino (alkylphosphino g wherein the C1-C5 alkyl group may be substituted or unsubstituted, and In addition, in the above Chemical Formula 2A, n1 and n2 may be linear or branched alkyl groups. When n2 is 2 or more, L1 and / or L2 are mutually related among the examples above. In one example, when the sum of n1 and n2 is 2 or more, L1 and L Two of the 2 are M a and a heterocyclyl or heteroaryl bonded to can be formed. Z1, Z2, L1, or L2 and M a Each bond between Regardless, the bond may be covalent or coordinate.

[0054] The organic monolayer O1 may be represented by the following Chemical Formula 3, wherein m1 in Chemical Formula 1A is When l1 is 2 or more, the organic monomolecules O1 in each layer may be the same or different. It's fine.

[0055] [ka] In the above formula 3, one of the * represents a functional group in the lower layer or a functional group in the lower monolayer. The remaining one may be a bond to a functional group in the upper layer or a functional group in the upper monolayer. In this case, the bond may be, for example, a covalent bond. X b is O, S, Se, NR (R is H or CH3) or PR (R is H or CH3) It's possible.

[0056] In one example, MR in Formula 3 may be a substituted or unsubstituted aromatic ring. The substitution can be the replacement of hydrogen atoms on the aromatic ring with various functional groups. In some cases, Z3 and Z4, independently of each other, are a bond or a C1-C5 substitution or It can be an unsubstituted, linear or branched alkylene group, where substitution occurs at the alkyl The hydrogen of the hydroxyl group is OH, SH, SeH, NR2 (R is independently H or CH3) or may be substituted with PR2 (R independently of each other is H or CH3).

[0057] In another example, MR in Formula 3 is a C1-C18 substituted or unsubstituted alkyl group, The alkylene group may be linear or branched. The substitution occurs when a hydrogen atom in the alkylene group is substituted by radiation. functional groups capable of cross-linking, for example, substitution with functional groups including vinyl groups or OH, SH, SeH, NR2 (R is H or CH3, regardless of each other) or PR2 (R is H or CH3, regardless of each other) and MR is an alkylene group. In some cases, Z3 and Z4 may be a bond.

[0058] The multilayer molecular film photoresist 30 further includes a photoreactive layer FL2 in addition to the light absorbing layer FL1. The photoreactive layer FL2 may further include a layer structure represented by the following chemical formula 1B: It can have.

[0059] [ka] In the above formula 1B, one of the * represents a functional group in the lower layer or a lower monomolecular functional group. The other bond may be to a functional group in the upper layer or to a functional group in the upper monolayer. The bond may be a covalent bond, for example, to a functional group. M2 is a photoreactive inorganic single molecule, for example, Zr, Al, Hf, Zn, or In. m2 may be an organometallic monolayer containing O2, and m2 may be an organic monolayer containing O2. n2 may be 1 to 10, and l2 may be 1 to 1000. Specifically, m2 may be 1 to 2, for example, m2 may be 1. n2 may also be 1 to 2, as an example, n2 can be 1.

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

[0061] [ka] In the above formula 2B, one of the * represents a functional group in the lower layer or a lower monomolecular functional group. The other bond may be to a functional group in the upper layer or to a functional group in the upper monolayer. The bond may be a covalent bond, for example, to a functional group. Z1 and Z2 are independently a bond, a C1-C20 substituted or unsubstituted linear or is a branched alkylene group, a C1-C20 substituted or unsubstituted linear or branched alkylene oxide, C1-C20 substituted or unsubstituted linear or branched alkyleneamino, C1 C1-C20 substituted or unsubstituted linear or branched alkylenesilylamino substituted or unsubstituted linear or branched alkylene thio, C1-C20 substituted or unsubstituted Substituted linear or branched alkyleneseleno, or C1-C20 substituted or unsubstituted linear Or it can be a branched alkylenephosphino. b is a metal atom, specifically, It can be Zr, Al, Hf, Zn, or In. a are O, S, Se, NR (R is H or CH3) or PR (R is H or CH3).

[0062] L3 and L4 are M b The number of ligands bound to the The sum of these is M b can be determined by the coordination number resulting from the equation. For example, n1 and n The sum of L3 and L4 can be an integer from 1 to 4. L3 and L4 are independently a halogen group (ex Cl, Br, or I), C1-C5 alkyl groups, C1-C5 alkylsilylamino groups a C1-C5 alkoxy group, a C1-C5 alkylthio group, a C1-C5 alkyl Seleno group, C1-C5 alkylamino group, or C1-C5 alkylphosphine group Here, the C1-C5 alkyl group may be a substituted or unsubstituted, linear or In addition, in the above Chemical Formula 2B, n1 and / or n2 may be a branched alkyl group. If there are two or more, L3 and / or L4 may be selected from the above examples, regardless of each other. In one example, if the sum of n1 and n2 is 2 or more, two of L3 and L4 These are attached M b and form a heterocyclyl or heteroaryl. Z1, Z2, L3, or L4 and M b Each bond between It may be a bond or a coordinate bond.

[0063] The organic monomolecules O2 may be represented by the chemical formula 3. In the above-mentioned chemical formula 1B, m2 may be the same as or different from the organic monomolecule O1. When l2 is 2 or more, the organic monomolecules O2 in each layer may be the same or different. It's fine.

[0064] The photo-reactive inorganic monomolecules M2 and M3 are generated by the secondary electrons generated in the light-absorbing layer FL1 or by the photo-reactive inorganic monomolecules M2 and M3. and / or by secondary electrons generated by the metal contained in the following etching-resistant inorganic monomolecules M3. Thus, a cross-linking bond can be formed between the photoreactive inorganic single molecules M2 in the adjacent molecular beams ML. Specifically, the M between adjacent photoreactive inorganic monomolecules M2 b -L4 and L3-M b The bond reacts with the secondary electrons to form M b -Y2-M b can form bonds Such M b -Y2-M b The bond is formed by the multilayer molecular photoresist formed by exposure. A phenomenon agent that causes the pattern to appear, for example, a phenomenon gas or a phenomenon plasma. For this reason, the M b The type of where Y2 can be O, S, Se, N, or P.

[0065] However, the present invention is not limited to this, and the secondary electrons generated in the light absorption layer FL1 may Cross-linking can also be formed between light-absorbing inorganic monomolecules M1 in adjacent molecular beams ML. Specifically, M between the adjacent light-absorbing inorganic monomolecules M1 a -L2 and L1-M a Conclusion In this case, the reaction occurs due to the secondary electrons, and M a -Y1-M a A bond can be formed. This bond may also not be etched by the developing agent. It can be e, N, or P.

[0066] The multilayer molecular film photoresist 30 includes an etching-resistant layer FL1 in addition to the light-absorbing layer FL1. The etching-resistant layer FL3 may further include a compound represented by the following chemical formula 1C: The layer structure may be such that:

[0067] [ka] In the above formula 1C, one of the * represents a functional group in the lower layer or a lower monomolecular inner group. The other bond may be to a functional group in the upper layer or to a functional group in the upper monolayer. The bond may be a covalent bond, for example, to a functional group. M3 is an etching-resistant inorganic monolayer, for example, Al, Ti, Cu, W, or Z. n, and O3 can be an organic monolayer. , n3 may be 0 to 10, and l3 may be 1 to 1000. Specifically, m3 may be 1 to 2, for example, m3 may be 1. 3 can be 1 to 2, for example, n3 can be 1.

[0068] The etching-resistant inorganic monolayer M3 is an etching-resistant organic metal represented by the following chemical formula 2C. In the formula 1C, n3 is 2 or more, or l3 is 2 or more. In this case, the etching-resistant inorganic monomolecules M3 in each layer may be the same as or different from each other.

[0069] [ka] In the formula 2C, one of the * represents a functional group in the lower layer or a lower monomolecular functional group. The other bond may be to a functional group in the upper layer or to a functional group in the upper monolayer. The bond may be a covalent bond, for example, to a functional group. Z1 and Z2 are independently a bond, a C1-C20 substituted or unsubstituted linear or is a branched alkylene group, a C1-C20 substituted or unsubstituted linear or branched alkylene oxide, C1-C20 substituted or unsubstituted linear or branched alkyleneamino, C1 C1-C20 substituted or unsubstituted linear or branched alkylenesilylamino substituted or unsubstituted linear or branched alkylene thio, C1-C20 substituted or unsubstituted Substituted linear or branched alkyleneseleno, or C1-C20 substituted or unsubstituted linear Or it can be a branched alkylenephosphino. c is a metal atom, specifically, It can be Al, Ti, W, Zn, or Cu. a is O, S, Se, NR (R is H or or CH3) or PR (R is H or CH3).

[0070] L5 and L6 are M c The number of ligands bound to the The sum of these is M c can be determined by the coordination number resulting from the equation. For example, n1 and n The sum of L5 and L6 can be an integer of 1 to 4. L5 and L6 are independently a halogen group (ex Cl, Br, or I), C1-C5 alkyl groups, C1-C5 alkylsilylamino groups a C1-C5 alkoxy group, a C1-C5 alkylthio group, a C1-C5 alkyl Seleno group, C1-C5 alkylamino group, or C1-C5 alkylphosphine group Here, the C1-C5 alkyl group may be a substituted or unsubstituted, linear or In addition, in the above Chemical Formula 2C, n1 and / or n2 may be a branched alkyl group. If there are two or more, L5 and / or L6 may be selected from the above examples, regardless of each other. In one example, if the sum of n1 and n2 is 2 or more, two of L5 and L6 These are attached M c and form a heterocyclyl or heteroaryl. Z1, Z2, L5, or L6 and M c Each bond between It may be a bond or a coordinate bond.

[0071] The organic monolayer O3 may be represented by the chemical formula 3. The organic monolayer O3 is The organic monomolecules O3 in the absorption layer FL1 and O2 in the photoreaction layer FL2 are the same. In the above-mentioned Chemical Formula 1C, m3 is 2 or more or l3 is 2. In the above cases, the organic monomolecules O3 in each layer may be the same or different.

[0072] The photo-reactive inorganic monomolecules M2 and M3 are generated by the secondary electrons generated in the light-absorbing layer FL1 or by the photo-reactive inorganic monomolecules M2 and M3. and / or secondary electrons generated by the metal contained in the etching-resistant inorganic monomolecules M3. Cross-linking can be formed between the etching-resistant inorganic monomolecules M3 in the adjacent molecular beams ML. Specifically, M in the etching-resistant inorganic monomolecules M3 adjacent to each other can be c -L5 or M c The -L6 bond reacts with the secondary electrons to form M c -Y3-M c Forming a bond This kind of M c -Y 3 -M c The bond is not etched by the developing agent. Also, an etching agent for etching the etching target layer 20 may be, for example, For this reason, the M c Types of wherein Y can be O, S, Se, N, or P.

[0073] FIG. 2 shows a multilayer molecular film photoresist having a vertical molecular beam structure according to one embodiment of the present invention. 10 is a schematic diagram showing another example of the light absorbing layer.

[0074] The light absorbing layer FL1 shown in FIG. 2 is the same as that shown in FIG. 1 when m1 is 1, n1 is 1, and l1 is 2. 2, the light absorbing layer FL1 is illustrated as an example, but the light reactive layer FL2 and The etching-resistant layer FL3 and / or the etching-resistant layer FL4 may also have one of such exemplary structures. can.

[0075] Thus, in the above chemical formula 1, 1A, 1B, or 1C, m, m1, m2, m3 When n, n1, n2, and n3 are all 1, the multilayer molecular film photoresist 30 is an inorganic monolayer. Alternating products of molecules MM, M1, M2, or M3 with organic monomolecules OM, O1, O2, or O3 It can have a layered structure, in which case the inorganic monomolecules MM, M1, M2, or M3 Between each of these, an organic monomolecule, OM, O1, O2, or O3, is placed, and an inorganic monomolecule, MM, M1 , M2, or M3 and the organic monomolecules OM, O1, O2, or O3 all form the bottom (monolayer) layer. As a result, the molecular beams ML can be self-organized in a state where they are spaced apart from each other. They may extend upward relative to the substrate 10, for example, in a vertical direction.

[0076] 3 to 7 are schematic diagrams sequentially illustrating a photolithography method according to one embodiment of the present invention. 3 to 7, for convenience of explanation, the multilayer molecular film photoresist 30 is the same as that shown in FIG. For example, let us consider the case where 1, n2, n3, m1, m2, m3, l1, l2, and l3 are all 1. In chemical formulas 2A, 2B, and 2C, Z1 represents inorganic single molecules M1, M2, and M3. and Z2 are all bonds, and n1 and n2 are all 1.

[0077] Referring to FIG. 3, a substrate 10 having a layer to be etched 20 formed thereon can be provided. The substrate 10 and the layer to be etched 20 may be the same as those described with reference to FIG.

[0078] A multilayer molecular film photoresist 30 may be formed on the etching layer 20 . The multilayer molecular film photoresist 30 is described with reference to FIG. 1 except as described below. In one embodiment, the multilayer molecular film photoresist 30 is The etching-resistant layer FL3, the light-absorbing layer FL1, and the light-reactive layer FL2 are laminated in this order. However, the stacking order is not limited to this, and the stacking order may be the order of the layer to be etched 20. Depending on the type of material and / or the type of pattern to be formed through photolithography, The multilayer molecular film photoresist 30 can be formed by atomic layer deposition equipment or It can be formed using molecular layer deposition equipment.

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

[0080] In one example, the light-absorbing layer FL1 is formed by forming a light-absorbing metal monolayer M1 and an organic The molecular layer O1 is formed by repeating a cycle (11 in Chemical Formula 1A) multiple times, which includes the step of forming the molecular layer O1. In the step of forming the organic molecular layer O1, an organic precursor may be dosing, and the organic precursor may be added to the lower layer. an organic precursor dosing step in which precursors are chemically bonded in a self-assembly manner; and a purge gas and a purge stage for purging unreacted organic precursors and reaction products. You can perform the Kuru.

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

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

[0083] [ka] In the above formula 4, R a1 and R a2 are hydrogen or C1-C2 independently of each other. may be an alkyl group, and X b and X aare independent of each other, O, S, Se, NR( R can be H or CH3) or PR (R can be H or CH3). and MR are as defined in Chemical Formula 3 above.

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

[0085] [ka]

[0086] [ka]

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

[0088] [ka] In the above reaction formula 1, R0 is a functional group on the surface of the lower layer, and R0 is hydrogen, hydrochloride, or the like. oxy group, thiol group, amine group, phosphine group, C C1-C5 alkyl group, C1-C5 alkoxy, C1-C5 alkylthio group, C1- C5 alkylseleno group, C1-C5 alkylamine group, or C1-C5 alkyl R may be a phosphino group. a1 X b -Z3-MR-Z4-X a R a2 is an organic precursor and each functional group is as defined in Chemical Formula 4 above.

[0089] Referring to Reaction Scheme 1, the organic precursor reacts with the functional groups on the surface of the underlayer to form a film on the underlayer. In this process, R0R a1 can be produced as a reaction by-product. In the purge step, the remaining organic precursor and the reaction by-products can be purged.

[0090] In the step of forming the light-absorbing metal monolayer M1, a metal precursor is doped and the metal precursor is deposited on the lower layer. a metal precursor dosing step in which the precursors are chemically bonded in a self-assembly manner; and a purge gas and a purge stage for purging unreacted metal precursors and reaction products. Here, the purge gas can be argon.

[0091] The metal precursor for forming the light-absorbing metal monolayer M1 is represented by the following chemical formula 5A: obtain.

[0092] [ka] In the above formula 5A, R b1 and R b2 are independent of each other and are halogen groups (e.g., C l, Br, or I), a C1-C5 alkyl group, a C1-C5 alkylsilylamino group , C1-C5 alkoxy, C1-C5 alkylthio group, C1-C5 alkylseleno group, a C1-C5 alkylamino group, or a C1-C5 alkylphosphino group. Here, the C1 to C5 alkyl group is a substituted or unsubstituted linear or branched alkyl group. Z1, Z2, L1, L2, n1, n2, and M a is defined in Formula 2A In addition, in some cases, b1 , R b2 , L1, and L2 Two of them are directly or indirectly bonded to M aand heterocyclyl or heteroaryl Alternatively, R b1 and R b2 At least one of the a It may be coordinated to

[0093] Specific examples of metal precursors for forming the light-absorbing metal monolayer M1 include: is.

[0094] [ka]

[0095] [ka] In the metal precursor, R1, R2, R3, and R4 are independently selected from C1 to C 5 alkyl groups.

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

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

[0098] Unlike the illustration, when the light absorbing layer FL1 is formed of a number of metal monolayers M1 ( (When n1 in Chemical Formula 1A is 2 or more), a metal precursor dosing compound according to Reaction Scheme 2 described above is prepared. After the dosing step and the purging step, a reaction gas is dosed to chemically bond the lower layer. a reaction gas dosing stage in which the reactant gas reacts with the metal precursor; and a purge gas is supplied to remove the unreacted metal precursor. A unit cycle including a purge step for purging the reaction gas and reaction products is repeated. In this case, the reactive gas may be a gas containing hydrogen and oxygen (e.g., O2, O3, H2O ), a gas containing nitrogen (e.g., NH3), etc.

[0099] On the light absorbing layer FL1 or before forming the light absorbing layer FL1, a light reflecting layer is formed on the substrate. The photoreactive layer FL2 can be formed by atomic layer deposition. Specifically, the deposition can be carried out by using a molecular layer deposition method.

[0100] For example, the photoreactive layer FL2 is formed by a process of forming a photoreactive metal monolayer M2 and an organic compound. The organic molecular layer O2 may be formed by performing a cycle including a step of forming the organic molecular layer O2. The step of forming the organic molecular layer O1 is the same as or similar to the method of forming the light absorbing layer FL1. can be formed using a similar method, except that the organic precursor dosing of Scheme 1 In this step, -R0 is the metal precursor self-assembled on the underlayer as described in Reaction Scheme 2. The terminal group -R b2 The step of forming the photoreactive metal monolayer M2 may be Metal precursors are doped and chemically bonded to the lower layer in a self-organizing manner. Precursor dosing stage; and supplying purge gas to remove unreacted metal precursors and reaction products. A unit cycle can be performed that includes a purge stage for purging materials. The gas may be argon.

[0101] The metal precursor for forming the photoreactive metal monolayer M2 is represented by the following chemical formula 5B: obtain.

[0102] [ka] In the above formula 5B, R b1 and R b2 are independent of each other and are halogen groups (e.g., C l, Br, or I), a C1-C5 alkyl group, a C1-C5 alkylsilylamino group , C1-C5 alkoxy, C1-C5 alkylthio group, C1-C5 alkylseleno group, a C1-C5 alkylamino group, or a C1-C5 alkylphosphino group. Here, the C1-C5 alkyl group may be substituted or unsubstituted, and linear or branched. Z1, Z2, L3, L4, n1, n2, and M can be alkyl groups. b is chemical formula 2 B. In addition, in some cases, R b1 , R b2 , L3, and Two of L4 and L5 are directly or indirectly linked to Mb, forming heterocyclyl or heterocyclic rings. Alternatively, R b1 and R b2 At least one of is M b It may be coordinated to

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

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

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

[0106] Unlike the illustration, when the photoreactive layer FL1 is formed of a number of metal monolayers M2 ( (When n2 in Chemical Formula 1B is 2 or more), a metal precursor dosing compound according to Reaction Scheme 3 described above is prepared. After the dosing step and the purging step, a reaction gas is dosed to chemically bond the lower layer. a reaction gas dosing stage in which the reactant gas reacts with the metal precursor; and a purge gas is supplied to remove the unreacted metal precursor. A unit cycle including a purge step for purging the reaction gas and reaction products is repeated. In this case, the reactive gas may be a gas containing hydrogen and oxygen (e.g., O2, O3, H2O ), a gas containing nitrogen (e.g., NH3), etc.

[0107] On the light absorbing layer FL1 or before forming the light absorbing layer FL1, an erodesiccant-resistant layer is formed on the substrate. The etching-resistant layer FL3 can be formed. The deposition can be performed by atomic layer deposition, specifically molecular layer deposition.

[0108] In one example, the etching-resistant layer FL3 is formed as an etching-resistant metal monolayer M3. The organic molecular layer O3 may be formed by performing a cycle including the steps of forming the organic molecular layer O4 and forming the organic molecular layer O5. The step of forming the organic molecular layer O3 is the same as the step of forming the organic molecular layer O1 described in the light absorbing layer FL1. The organic precursor of Reaction Scheme 1 can be formed by a method identical to or similar to the method of Reaction Scheme 1. In the dosing step, -R0 may be a surface functional group attached on the surface of the etched side. do.

[0109] The step of forming the etching-resistant metal monolayer M3 is performed by dosing a metal precursor onto the lower layer. a metal precursor dosing step in which the metal precursor is chemically bonded to the polymer in a self-assembly manner; and A purge stage is provided in which a digas is supplied to purge unreacted metal precursors and reaction products. A unit cycle can be performed, where the purge gas can be argon.

[0110] The metal precursor for forming the etching-resistant metal monolayer M3 is represented by the following chemical formula 5C: It can be represented as:

[0111] [ka] In the above formula 5C, R b1 and R b2 are independent of each other and are halogen groups (e.g., C l, Br, or I), a C1-C5 alkyl group, a C1-C5 alkylsilylamino group , C1-C5 alkoxy, C1-C5 alkylthio group, C1-C5 alkylseleno group, a C1-C5 alkylamino group, or a C1-C5 alkylphosphino group. Here, the C1-C5 alkyl group may be substituted or unsubstituted, and linear or branched. Z1, Z2, L5, L6, n1, n2, and M can be alkyl groups. c is chemical formula 2 C. In addition, in some cases, R b1 , R b2 , L5, and Two of L6 and L7 are directly or indirectly linked to M c and bonded to a heterocyclyl or hetero Alternatively, R b1 and R b2 At least one of is M c It may be coordinated to

[0112] Specific examples of metal precursors for forming the etching-resistant metal monolayer M3 include the following: That's right.

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

[0114] [ka] In the reaction formula 4, -X a R a2 is the surface functional group of the lower layer, specifically, The metal precursor of formula 5C is the surface functional group of the organic molecular layer O3 formed above. They can react with the surface functional groups of the organic molecular layer O3 and self-assemble on the surface of the organic molecular layer O3. In this process, R a2 Rb1 can be produced as a reaction by-product. In Reaction Scheme 4, the metal precursor and the reaction by-products can be purged. The functional groups can be the same as those defined in Formula 4 and Formula 5C.

[0115] Unlike the illustration, the etching-resistant layer FL1 is formed of a number of metal monolayers M3. In this case (when n3 in Chemical Formula 1C is 2 or more), the metal precursor dopant is reacted with the metal precursor dopant according to Reaction Formula 4 described above. After the dosing step and the purging step, a reaction gas is dosed to the lower layer. a reactant gas dosing step for reacting with the bonded metal precursor; and a purge gas supply step. A unit cycle including a purge step for purging unreacted reaction gas and reaction products is repeated. In this case, the reaction gas is a gas containing hydrogen and oxygen (e.g., O2, O3, H2O), nitrogen-containing gas (e.g., NH3), etc.

[0116] However, without being limited to the above, in another embodiment of the present invention, the multilayer molecular film The photoresist 30 is formed by forming a metal monolayer (MM in Chemical Formula 1) and an organic monolayer (Chemical Formula 1). The organic molecule may be formed by performing a cycle including the step of forming OM) of Formula 1. The step of forming the layer (OM of Chemical Formula 1) is performed by dosing the organic precursor of Chemical Formula 4, an organic precursor dosing step in which the organic precursor is chemically bonded to the sublayer in a self-assembly manner; and A purge stage is provided to supply a purge gas and purge unreacted organic precursors and reaction products. A unit cycle can be performed in which the purge gas can be argon. In the organic precursor dosing step, the reaction according to Reaction Scheme 1 can occur.

[0117] The step of forming the metal monolayer (MM of Formula 1) is carried out by using a metal precursor of Formula 5 below: Metal precursor dosing is performed by dosing the metal precursor onto the lower layer, and the metal precursor is chemically bonded to the lower layer in a self-organizing manner. and a purge gas is supplied to purge unreacted metal precursors and reaction products. A unit cycle can be performed with a purge stage in which the purge gas is argon. It could be.

[0118] [ka] In the above formula 5, R b1 and R b2 are not related to each other and are halogen groups (e.g., Cl , Br, or I), a C1 to C5 alkyl group, a C1 to C5 alkylsilylamino group, C1-C5 alkoxy, C1-C5 alkylthio group, C1-C5 alkylseleno group , a C1-C5 alkylamino group, or a C1-C5 alkylphosphino group. Here, the C1 to C5 alkyl group is a substituted or unsubstituted linear or branched alkyl group. Z1, Z2, L a , L b , na, nb, and M 0 is defined in Chemical Formula 2 In addition, in some cases, b1 , R b2 , L a , and L b Of The second is M, which is directly or indirectly bonded to these. 0 and a heterocyclyl or heteroaryl bonded to Alternatively, R b1 and R b2 At least one of the 0 Coordinated to It may be in a combined state.

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

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

[0121] Specifically, the metal precursor may be represented by the above-mentioned chemical formula 5A, 5B, or 5C. Specifically, the reaction according to Reaction Scheme 2, 3, or 4 occurs in the metal precursor dosing step. It can happen.

[0122] Referring to FIG. 4, a portion of the multilayer molecular film photoresist 30 is irradiated with radiation hv, specifically, In this case, the light absorbing layer FL1 can be irradiated with EUV or E beam. d orbitals, for example, metal atoms having 4d or 5d orbitals, M a teeth, The radiation can be absorbed to generate secondary electrons. First, metal atoms or Other elements can also absorb radiation and produce secondary electrons.

[0123] The secondary electrons generated in the light absorption layer FL1 are used to induce photoreactive inorganic compounds in the adjacent molecular beam ML. A cross-linking bond can be formed between the single molecules M2. M in reactive inorganic monomolecules M2 b -L4 and L3-M b reacts with the secondary electrons to form M b -Y2-M b A bond can be formed, where Y2 is O, S, Se, N, or or P. In addition, the secondary electrons generated in the light absorption layer FL1 can Cross-linking can also be formed between the light-absorbing inorganic monomolecules M1 in the sagittal line ML. is M in the light-absorbing inorganic monomolecule M1 a -L2 and L1-M a The bond is formed by the secondary electrons. And he responded, "M" a -Y1-M a A bond can be formed, where Y1 is O, S , Se, N, or P. Also, the secondary electrons generated in the light absorption layer FL1 This allows forming cross-links between the etching-resistant inorganic monomolecules M3 in the adjacent molecular beams ML. Specifically, M in the etching-resistant inorganic monomolecules M3 c -L6 and L5-M c The bond reacts with the secondary electrons to form M c -Y3-M c can form bonds wherein Y3 can be O, S, Se, N, or P.

[0124] Referring to FIG. 5, the multilayer molecular film photoresist 30 exposed to radiation is treated with a developing agent. In this case, the inorganic single molecules M1, M2, and M3 are also removed by the developing agent except for the part where cross-linking is formed. A multilayer molecular film photoresist pattern 31 can be formed. Solutions, such as water, isopropyl alcohol (IPA), methyl isobutyl ketone ( MIBK), tetramethylammonium hydroxide (TMAH), or a gas for the process, for example The gas may be CF4, Ar, O2, CHF3, etc., or a plasma generated from these.

[0125] Referring to FIG. 6, the multilayer molecular film photoresist pattern 31 is used as a mask to perform etching. The etching can be performed by plasma etching, for example. In this case, M between the etching-resistant inorganic monomolecules M3 c -Y3-M c join This increases the etching resistance of the multilayer molecular film photoresist pattern 31, The membrane 20 can be selectively etched.

[0126] Referring to FIG. 7, the multilayer molecular film photoresist pattern 31 can be removed. This can be done using an ashing method.

[0127] Further referring to FIG. 3, a molecular layer deposition apparatus for manufacturing a multilayer molecular film photoresist will be described. Except as noted below, the description will be given with reference to Figures 1, 2a, 2b, and 3. We will refer to the explanation given above.

[0128] The molecular layer deposition equipment according to one embodiment of the present invention forms a metal monolayer (MM of Formula 1). and forming an organic molecular layer (OM of Formula 1) are repeated multiple times. In practice, the number of times indicated by 1 in Chemical Formula 1 can be repeated. The step of forming the organic precursor (OM) is performed by dosing the organic precursor of Formula 4 onto the lower layer. an organic precursor dosing step that chemically bonds the molecules in a self-assembly manner; and a purge gas supply step. and a purge step for purging unreacted organic precursors and reaction products. Here, the purge gas may be argon. In the cleaving step, the reaction according to Reaction Scheme 1 can occur.

[0129] The step of forming the metal monolayer (MM of Formula 1) is carried out by using a metal precursor of Formula 5. Metal precursor dosing is performed by dosing the metal precursor onto the lower layer, and the metal precursor is chemically bonded to the lower layer in a self-organizing manner. and a purge gas is supplied to purge unreacted metal precursors and reaction products. A unit cycle can be performed with a purge stage in which the purge gas is argon. In the metal precursor dosing step, the reaction according to Reaction Scheme 5 may occur. Specifically, the metal precursor may be represented by the above-mentioned chemical formula 5A, 5B, or 5C. Specifically, the reaction according to Reaction Formula 2, 3, or 4 occurs in the metal precursor dosing step. I can get used to it.

[0130] The molecular layer deposition apparatus according to an embodiment of the present invention is specifically configured to deposit a light-absorbing metal monolayer on a substrate. A cycle including a step of forming a layer M1 and a step of forming an organic molecular layer O1 is repeated multiple times, specifically In this case, the light absorbing layer FL1 can be formed by performing the process as many times as indicated by 11 in Chemical Formula 1A. .

[0131] In the step of forming the organic molecular layer O1, the organic precursor of the formula 4 is doped, and the lower an organic precursor dosing step in which the organic precursor is chemically bonded to the layer in a self-assembly manner; and a purge stage for supplying a purge gas to purge unreacted organic precursors and reaction products; Here, the purge gas may be argon. In the organic precursor dosing step, the reaction according to Reaction Scheme 1 may occur.

[0132] The step of forming the light-absorbing metal monolayer M1 is carried out by doping the metal precursor of Formula 5A. A metal precursor dosing step is performed in which the metal precursor is chemically bonded to the lower layer in a self-organizing manner. and a purge gas supply to purge unreacted metal precursors and reaction products. A unit cycle can be performed comprising a purge stage, where the purge gas is argon. In the metal precursor dosing step, the reaction according to Reaction Scheme 2 may occur.

[0133] On the light absorbing layer FL1 or before forming the light absorbing layer FL1, a light reflecting layer is formed on the substrate. A cycle including a step of forming a metal monolayer M2 and a step of forming an organic monolayer O2 is repeated. Specifically, the number of times indicated by 12 in Chemical Formula 1B is repeated to form a photoreactive layer FL2. The step of forming the organic molecular layer O2 can be performed in the same manner as described for the light absorbing layer FL1. The electrodes can be formed using one or similar methods.

[0134] The step of forming the photoreactive metal monolayer M2 is performed by dosing the metal precursor of Formula 5B. a metal precursor dosing step in which the metal precursor is chemically bonded to the lower layer in a self-organizing manner; and a purge stage in which a purge gas is supplied to purge unreacted metal precursors and reaction products. A unit cycle comprising steps can be performed, where the purge gas can be argon. In the metal precursor dosing step, the reaction according to Reaction Scheme 3 may occur.

[0135] On the light absorbing layer FL1 or before forming the light absorbing layer FL1, an erodesiccant-resistant layer is formed on the substrate. A cycle including a step of forming an etching metal monolayer M3 and a step of forming an organic monolayer O3 The etching-resistant layer FL3 is formed by repeating the etching process several times, specifically, the number of times indicated by 13 in Chemical Formula 1C. The step of forming the organic molecular layer O3 can be performed in the same manner as described above for the light absorbing layer FL1. The above-described method can be used to form the same or similar to the method described above.

[0136] The step of forming the etching-resistant metal monolayer M3 is performed by doping the metal precursor of Formula 5C. Metal precursor dosing is performed by chemically bonding the metal precursor to the lower layer in a self-organizing manner. and a purge gas is supplied to purge unreacted metal precursors and reaction products. A unit cycle can be performed comprising a purge step, where the purge gas is argon. In the metal precursor dosing step, the reaction according to Reaction Scheme 4 may occur.

[0137] As described above, the multilayer molecular film photoresist 30 according to one embodiment of the present invention is The formation of inorganic and organic molecules that are connected by bonds within the molecule through self-assembly. This allows each molecular beam to grow upward from the substrate, and also allows the molecular beam to grow laterally. can be uniformly arranged.

[0138] In this case, the distance between the molecular beams (D in FIG. 1 or FIG. 4) is 1 nm or less, specifically, 0.5 nm. It is extremely small, less than 1000 m. In addition, it is possible to separate non-particle molecular beams during exposure and development. Therefore, the line edge roughness (Line Edge Roughness) means the roughness of the side surface of the pattern. The LER (Linear Emission Ratio) is very low at 1.2 nm or less, and the resolution n) can be significantly improved to 6 nm or less. The 30th generation of 4d or 5d inorganic atoms has a high optical absorption rate for EUV. A light-absorbing inorganic single molecule M1 having a metal atom with orbitals, and a low photon density EU Although the probability of stochastic failure is low for V, High light sensitivity (ex. 10mJ / cm 2 ) can be shown.

[0139] Below, preferred examples are presented to aid in understanding the present invention. However, the following experimental examples are merely intended to aid in the understanding of the present invention, and the present invention is not limited to the following examples. The present invention is not limited by the examples.

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

[0141] Referring to FIG. 8, DEZ (diethylzinc) was injected into the chamber for 2 seconds. The chamber was purged for 30 seconds, water (H2O) was dosed for 2 seconds, and the chamber was then purged for 30 seconds. The chamber was purged 30 times to form a ZnO inorganic molecular layer. Successful.

[0142] FIG. 9 shows a pattern of the vertically designed inorganic multilayer molecular photoresist formed with reference to FIG. Specifically, the SEM image was taken after the scanning. 100kV voltage and 2500uC / cm on vertically designed inorganic multilayer molecular film 2 Nodo After irradiation with e-beam under se conditions, TMAH (tetramethylammonium hydroxide) The solution was decomposed by sonication in nH2O for 2 min.

[0143] Referring to FIG. 9, a pattern having a line width of 1 um and a pattern having a line width of 500 nm are It can be seen that the crystals are neatly formed.

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

[0145] Referring to FIG. 10, the substrate is loaded into the chamber and the substrate temperature is set to 100-30 0°C (specifically, 100 to 150°C), and an inorganic precursor, Hf precursor, (Tetrakisdimethylamido Hafnium), Ti precursor (Te trakisdimethylamido Titanium), Al precursor (Trim ethyl Aluminum), or DEZ (diethylzinc) at 0.01 Dosing was performed for 1 second at a pressure of ~10 torr (0.05 to 0.5 torr), followed by chafing for 5 seconds. The chamber was purged, and 4-mercaptophenol was added as the organic precursor at 0.01 to 10 torr. Dosing at 0.01 torr for 1 second and purging the chamber for 5 seconds. The photoresist was then subjected to multiple photolithography cycles (approximately 30 times) to form a multilayer molecular film photoresist approximately 20 nm thick. Formed.

[0146] 11a, 11b, and 11c are formed using the method described with reference to FIG. This is an SEM image taken after patterning the photoresist. , a voltage of 100 kV, 100 pA, and 2500uC / cm 2 After exposure to e-beam under the dose condition of TMAH( The mixture was decomposed by sonication in tetramethylammonium hydroxide (TMAH) in H2O for 2 minutes.

[0147] Referring to Figures 11a, 11b, and 11c, half pitch It can be seen that a pattern with a line width of 500 nm was clearly formed. The pattern is formed in the exposed area, and the photoresist according to this embodiment is a negative type. It can be defined as a reactive photoresist.

[0148] FIG. 12 shows an electron beam of photoresist formed using the method described with reference to FIG. 11 is a graph showing sensitivity to the photoresist formed with reference to FIG. Voltage of 100kV, 100pA and 1-10,000uC / cm on the test strip 2 dose After exposure to e-beam under the conditions, TMAH (tetramethylammonium hydroxide) ) in H2O for 2 minutes, and then the thickness of the pattern was measured according to the exposure dose. This was shown.

[0149] Referring to FIG. 12, the normalized thickness (nor (malized thickness) means that the thickness immediately after deposition is maintained even after the deposition. The multilayer molecular film photoresist formed using the Hf precursor exhibited the lowest It is the most sensitive by showing a normalized thickness of 1 nm at low e-beam doses. It turns out that there are.

[0150] FIG. 13a is a schematic diagram showing the form and dose conditions for EUV irradiation, and FIG. 13b is a schematic diagram showing the form and dose conditions for EUV irradiation. 13a was formed using the method described with reference to FIG. 10. The photoresist pattern obtained when irradiating a photoresist using a precursor was photographed. Specifically, FIG. 13a shows an optical photograph of the Hf precursor formed with reference to FIG. After exposing the photoresist to EUV as shown in Figure 13a, TMA Decomposed by sonication in tetramethylammonium hydroxide (H2O) for 2 minutes. This is a photo.

[0151] Referring to Figures 13a and 13b, the Hf precursor exhibits a thickness of approximately 20 nm as deposited. When a photoresist using this material is exposed to EUV, the radiation intensity is approximately 40 mJ / cm 2 The above When exposed to light and developed, it shows a thickness of about 10 nm or more. The EUV sensitivity of the photoresist using Hf precursor is 40 mJ / cm 2 Being You can see that.

[0152] FIG. 14a shows a flow diagram using a Zn precursor formed using the method described with reference to FIG. Atomic force microscopy (AFM) obtained after electron beam exposure and development of photoresist. e) microscopy image, and Fig. 14b shows the PMMA photoresist after electrodeposition. Atomic force microscope (AFM) images obtained after electron beam exposure and development. In this case, PMMA photoresist is made by dissolving PMMA in chlorobenzyl alcohol. After applying a solution of the material to the glass, it is irradiated with an electron beam and the irradiated area is removed by the electron beam. The electron beam irradiated the two photoresists at a common frequency of 10 Voltage: 0kV, 100pA, 2500uC / cm 2 Before Zn irradiation Photoresists using precursors include TMAH (tetramethylammonium hydroxide) in The film was sonicated in H2O for 2 minutes, and the unexposed areas were removed by development.

[0153] Referring to Figures 14a and 14b, photoresists using Zn precursors were found to be It can be seen that the line edge roughness is even lower than that of the MA photoresist.

Claims

1. A plurality of molecular beams are arranged laterally and each extending upwardly from the substrate, Each molecular beam is composed of a large number of inorganic monomolecules and at least some of the inorganic monomolecules. A multilayer molecular film photoresist in which organic monomolecules are interposed and connected by bonds.

2. The van der Waals gap between the organic monomolecules in the laterally adjacent molecular beams among the molecular beams The multilayer molecular film photoresist of claim 1 , wherein a molecular interaction is present.

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

4. Each of the molecular beams is formed by alternately stacking and bonding the inorganic monomolecules and the organic monomolecules.

2. The multilayer molecular film photoresist according to claim 1 .

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

6. The multilayer molecular film photoresist includes a light-absorbing layer including a light-absorbing inorganic monomer, a photo-reactive inorganic monomer, and a a photoreactive layer comprising an inorganic monolayer and an etching-resistant layer comprising an etching-resistant inorganic monolayer; The multilayer molecular film photoresist of claim 5 having at least one layer.

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

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

9. The photoreactive inorganic monolayer is an inorganic monolayer having a metal element selected from Zr, Al, Hf, Zn, and In. The multilayer molecular film photoresist of claim 6, which is an organic monolayer.

10. The etching-resistant inorganic monolayer has a metal element selected from Al, Ti, W, Zn, and Cu.

7. The multilayer molecular film photoresist according to claim 6, which is an inorganic monolayer.

11. A plurality of molecular beams are arranged laterally and each extending upwardly from the substrate, Each of the molecular beams is a multilayer molecular film photoresist having a layer represented by the following Chemical Formula 1: 【Chemistry 1】 In the formula 1, one of the *'s is a bond to a functional group in the lower layer, and the other one The first is bonding with functional groups in the upper layer, MM is an inorganic monomolecule containing a metal element, OM is an organic monomolecule, m is 1 to 2, n is 1 to 2, and l is 1 to 1000.

12. The organic monolayer photopolymer of claim 11, wherein the organic monolayer is represented by the following chemical formula 3: Resist: 【Chemistry 2】 In the formula 3, one of the *'s is a bond with a functional group in the lower layer, and the other one The first is bonding with functional groups in the upper layer, X ｂ is O, S, Se, NR (R is H or CH ３ ) or PR (R is H or CH ３ ) and MR is a substituted or unsubstituted aromatic ring or a C1-C18 substituted or unsubstituted is a linear or branched alkylene group, When MR is the aromatic ring, Z ３ and Z ４ are independent of each other, and are bonds or C a 1-C5 substituted or unsubstituted, linear or branched alkylene group; When MR is the alkylene group, Z ３ and Z ４ is a bond.

13. M is a light-absorbing inorganic monolayer containing a metal element with a d orbital, such as Zr, Al, Hf, Z Photoreactive inorganic monomolecules containing n or In, or Al, Ti, Cu, W, or Zn The multilayer molecular film photoresist according to claim 11, which is an etching-resistant inorganic monolayer comprising:

14. The layer represented by Chemical Formula 1 is a layer represented by Chemical Formula 1A below. Thin film photoresist: 【Transformation 3】 In the formula 1A, one of the *'s is a bond to a functional group in the lower layer, and the remaining One is bonding with functional groups in the upper layer, M1 is a light-absorbing inorganic monolayer containing a metal element with a d orbital; O1 is an organic monolayer, m1 is 1 to 2, n1 is 1 to 2, and l1 is 1 to 1000.

15. Each of the molecular beams is formed by depositing a layer represented by the following Chemical Formula 1B on or under the layer represented by the Chemical Formula 1A. The multilayer molecular film photoresist of claim 14, comprising: 【Chemistry 4】 In the formula 1B, one of the *'s is a bond to a functional group in the lower layer, and the remaining One is bonding with functional groups in the upper layer, M2 is a photoreactive inorganic monolayer containing Zr, Al, Hf, Zn, or In; O2 is an organic monomolecule, m2 is 1 to 2, n2 is 1 to 2, and l2 is 1 to 1000.

16. Each of the molecular beams is formed by depositing a layer represented by the following Chemical Formula 1C on or under the layer represented by the Chemical Formula 1A. The multilayer molecular film photoresist of claim 14, comprising: 【Transformation 5】 In the formula 1C, one of the *'s is a bond to a functional group in the lower layer, and the remaining One is bonding with functional groups in the upper layer, M3 is an etching-resistant inorganic monolayer containing Al, Ti, Cu, W, or Zn; O3 is an organic monolayer, m3 is 1 to 2, n3 is 1 to 2, and l3 is 1 to 1000.

17. The multilayer molecular film photoresist is an EUV photoresist.

12. The multilayer molecular film photoresist according to claim 11.

18. A plurality of molecular beams are arranged in the horizontal direction and extend upward from the substrate, The line is a multilayer molecular film photoresist having a layer represented by the following chemical formula 1, and The layer represented by Chemical Formula 1 is formed by forming a metal monolayer on a substrate and an organic monolayer. Multilayer molecular film photoresist deposition equipment that forms multiple cycles including the steps: 【Transformation 6】 In the formula 1, one of the *'s is a bond to a functional group in the lower layer, and the other one The first is bonding with functional groups in the upper layer, MM is an inorganic monomolecule containing a metal element, OM is an organic monomolecule, m is 1 to 2, n is 1 to 2, and l is 1 to 1000.

19. M is a light-absorbing inorganic monolayer containing a metal element with a d orbital, such as Zr, Al, Hf, Z Photoreactive inorganic monomolecules containing n or In, or Al, Ti, Cu, W, or Zn 19. The multilayer molecular film photoresist deposition of claim 18, wherein the multilayer molecular film photoresist deposition is an etch-resistant inorganic monolayer comprising Equipment.

20. The organic monolayer photopolymer of claim 18, wherein the organic monolayer is represented by the following chemical formula 3: Resist deposition equipment: 【Transformation 7】 In the formula 3, one of the *'s is a bond with a functional group in the lower layer, and the other one The first is bonding with functional groups in the upper layer, X ｂ is O, S, Se, NR (R is H or CH ３ ) or PR (R is H or CH ３ ) and MR is a substituted or unsubstituted aromatic ring or a C1-C18 substituted or unsubstituted is a linear or branched alkylene group, When MR is the aromatic ring, Z ３ and Z ４ are independent of each other, and are bonds or C a 1-C5 substituted or unsubstituted, linear or branched alkylene group; When MR is the alkylene group, Z ３ and Z ４ is a bond.

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