Patent Application
20250164873
This application claims priority to Korean Patent Application No. 10-2023-0161441, filed in the Korean Intellectual Property Office on Nov. 20, 2023, the disclosure of which is incorporated by reference herein in its entirety.
Due to the development of electronic technology, down-scaling of integrated circuit devices is rapidly progressing. Accordingly, a photolithography process that is advantageous for implementing fine patterns is desired.
In general, in some aspects, the present disclosure is directed toward a photoresist composition having improved process stability by suppressing changes over time in a photolithography process for manufacturing integrated circuit devices and provide improved etch resistance and resolution.
According to some aspects, the present disclosure is directed to a method of manufacturing an integrated circuit device that improves process stability by suppressing changes over time in the photolithography process and improves the dimensional precision of patterns to be formed by providing improved etch resistance and resolution.
According to some aspects, the present is directed to a photoresist composition including an organometallic compound including a central metal and at least one organic ligand bonded to the central metal, and a solvent, wherein the at least one organic ligand included in the organometallic compound includes an ylide group including an atom with a formal charge of −1 coordinately bonded to the central metal and a hetero atom with a formal charge of +1 bonded to the atom with a formal charge of −1.
According to some aspects, the present disclosure is directed to a photoresist composition including an organometallic compound including a central metal and a plurality of organic ligands bonded to the central metal, an organic ligand precursor, and a solvent, wherein the plurality of organic ligands included in the organometallic compound is a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group covalently or coordinately bonded to the central metal, and the organic ligand precursor is a C1 to C30 aliphatic hydrocarbon group including a first atom with a formal charge of −1 capable of a ligand substitution reaction with at least one of the plurality of organic ligands bonded to the central metal, and a second atom that is a hetero atom with a formal charge of +1 bonded to the first atom, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group including the first atom and the second atom.
According to some aspects, the present disclosure is directed to a method of manufacturing an integrated circuit device, the method including forming a photoresist film on a substrate using a photoresist composition including a central metal, an organometallic compound including a plurality of organic ligands bonded to the central metal, and a solvent, exposing a first region that is a part of the photoresist film, forming a metal structure network in the first region by inducing a desorption reaction of some of the plurality of organic ligands from the organometallic compound in the first region bybound baking the photoresist film including the exposed first region and by inducing a condensation reaction of a hydroxyl (OH) functional group generated at the site where some of the plurality of organic ligands among the organometallic compounds are desorbed, and forming a photoresist pattern including the metal structure network by developing the photoresist film on which the metal structure network is formed, wherein, in the forming of the photoresist film, at least one of the plurality of organic ligands includes an ylide group including a first atom and a second atom, wherein the first atom has a formal charge of −1 and is coordinated to the central metal, and the second atom is a heteroatom with a formal charge of +1 and is bonded to the first atom.
Example implementations will be more clearly understood from the following detailed description, taken in conjunction with the accompanying drawings.
Hereinafter, example implementations will be explained in detail with reference to the accompanying drawings.
Photoresist compositions may include an organometallic compound and a solvent. According to some implementations, the organometallic compound may include a central metal and at least one organic ligand bonded to the central metal. For example, the organometallic compound may include a central metal and at least one organic ligand coordinately or covalently bonded to the central metal.
In the photoresist composition, the central metal included in the organometallic compound may include at least one metal element. The at least one metal element may include a metal atom. In some implementations, the center metal may include at least one metal element selected from Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, and Fe, but the present disclosure is not limited to the above examples.
In the photoresist composition, the organic ligand included in the organometallic compound may include C1 to C30 aliphatic hydrocarbon group including a first atom with a formal charge of −1 that binds to the central metal and a second atom that is a heteroatom with a formal charge of +1 and is bonded to the first atom with a formal charge of −1, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group including the first atom and the second atom.
In the present disclosure, the C1 to C30 aliphatic hydrocarbon group including the first atom with a formal charge of −1 and a second atom that is a heteroatom with a formal charge of +1 and is bonded to the first atom with a formal charge of −1, or the substituted or unsubstituted C6 to C30 aromatic hydrocarbon group including the first atom and the second atom may be referred to as a ylide group. The ylide group may include, for example, phosphorus ylide, sulfur ylide, or nitrogen ylide. In present specification, an organic ligand including the ylide group may be referred to as a “ylide ligand.”
In some implementations, the organometallic compound may be represented by Formula 1 below.
M(A11)a(A12)b(A13)c(B11)d [Formula 1]
In Formula 1, M represents Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe,
In some implementations, the organometallic compound may be represented by Formula 2 below.
M(A11)a(A12)b(A13)c(A14)d [Formula 2]
In Formula 2, M represents Sn, Sb, In, Bi, Ag, Te, Au, Pb, Zn, Ti, Hf, Zr, Al, V, Cr, Co, Ni, Cu, Ga, Mn, Sr, W, Cd, Mo, Ta, Nb, Cs, Ba, La, Ce, or Fe,
As used herein, unless otherwise defined, the term “substituted” denotes that at least one hydrogen bonded to carbon is replaced with a substituent, or at least one carbon atom is replaced with a heteroatom including group. The substituent may include, for example, a halogen element, a hydroxy group, an aldehyde group, a carboxyl group, an amino group, a cyano group, an isocyanate group, a thiol group, a sulfonic acid group, a phosphoric acid group, a salt thereof, C1 to C20 alkyl, C1 to C20 cycloalkyl, C2 to C20 alkenyl, C1 to C20 alkoxy, C2 to C20 alkenoxy, C6 to C30 aryl, C6 to C30 aryloxy, C7 to C30 alkylaryl, or a C7 to C30 alkylaryloxy group. The hetero element-including group may be, for example, —O—, —C(═O)—O—, —O—C(═O)—, —C(═O)—, —O—C(═O)—O—, —C(═O)—NH—, —NH—, —S—, —S(═O)2—, or —S(═O)2—O—.
In some implementations, A11, A12, A13, and A14 may each not include the ylide group described above.
In some implementations, A11, A12, A13, and A14 are each a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group covalently bonded to M, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group covalently bonded to M. For example, hydrogen or carbon included in A11, A12, A13, and A14 may be covalently bonded to M. Hereinafter, when A11, A12, A13, and A14 are each hydrocarbon groups covalently bonded to M, A11, A12, A13, and A14 may be referred to as R11, R12, R13, and R14, respectively.
In some implementations, R11, R12, R13, and R14 may each be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or a substituted or unsubstituted phenyl group.
In some implementations, R11, R12, R13, and R14 may include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tertiary butyl group, a tertiary amyl group, a secondary butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.
In some implementations, R11, R12, R13, and R14 may include an aromatic ring. The aromatic ring may be a single aromatic ring such as benzene; a heteroaryl group such as pyridine, pyrimidine, thiophene, etc., or a condensed aryl group such as quinoline, isoquinoline, naphthalene, anthracene, and phenanthrene.
In some implementations, R11, R12, R13, and R14 may each include an acid group selected from a hydroxyl group, a sulfonate group, a carboxyl group, and a phosphonate group.
In some implementations, R11, R12, R13, and R14 may each include at least one selected from the following structural units. In the following structures, * is a binding position.
In some implementations, R11, R12, R13, and R14 may each include at least one structure selected from the following structural units.
In some implementations, R11, R12, R13, and R14 may each have the same structure. In some other embodiments, at least one selected from R11, R12, R13, and R14 may have a different structure from the others.
In some implementations, A11, A12, A13, and A14 may each include at least one hetero atom and may be a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group that are coordinated to the M. For example, at least one hetero atom included in A11, A12, A13, and A14 may coordinate to M. Hereinafter, when A11, A12, A13, and A14 each include at least one hetero atom as described above and are a hydrocarbon group coordinated to the M, A11, A12, A13, and A14 may be referred to as X11, X12, X13, and X14, respectively.
In some implementations, X11, X12, X13, and X14 may each be R21—O—*, R22—C(═O)—O—*, R23—O—C(═O)—*, R24—O—C(═O)—O—*, R25—N(R26)—*, R27—S—*, R28—S(═O)2—*, or R29—S(═O)2—O—*. Wherein, * is a binding site with M, and R21, R22, R23, R24, R25, R26, R27, R28, and R29 may each be independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or a substituted or unsubstituted phenyl group.
In some implementations, X11, X12, X13, and X14 may each include a hydrocarbyl group substituted with at least one heteroatom functional group including an oxygen atom, a nitrogen atom, a halogen atom, cyano, thio, silyl, ether, carbonyl, ester, nitro, amino, or any combination thereof. The halogen element may include F, Cl, Br, or I.
In some implementations, X11, X12, X13, and X14 may each include an acid group selected from a hydroxyl group, a sulfonate group, a carboxyl group, and a phosphonate group.
In some implementations, X11, X12, X13, and X14 may each include a CF3COO-ligand, a CF3SO3-ligand, a CF2CF2SO3-ligand, a CF3CF2(CF3)2CO-ligand, a CF3SO2-ligand, a para-toluenesulfonyl ligand, or a diethyl phosphate ligand.
In some implementations, X11, X12, X13, and X14 may each include an aromatic ring, a heteroaromatic ring, or any combination thereof. The aromatic ring may be a single aromatic ring such as benzene; a heteroaryl group such as pyridine, pyrimidine, thiophene, etc.; or a condensed aryl group such as quinolone, isoquinoline, naphthalene, anthracene, and phenanthrene, etc. The heteroaryl group and the condensed aryl group may include at least one hetero atom selected from oxygen (O), sulfur(S), and nitrogen (N).
In some implementations, X11, X12, X13, and X14 may each include a polydentate ligand. The polydentate ligand may include a bidentate ligand including two atoms capable of coordination, a tridentate ligand including three atoms capable of coordination, or a tetradentate ligand including four atoms capable of coordination, but is not limited thereto. For example, the polydentate ligand may include quinoline, β-diketonate, ethylenediaminetetraacetic acid (EDTA), 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP), salen: (2,2)ethylenebis (nitrilomethylidene)diphenol), norbornene dicarboxylic acid, camphoric acid, and a structure selected from derivatives thereof, but is not limited thereto.
In some implementations, X11, X12, X13, and X14 may each have the same structure. In some other example embodiments, at least one selected from X11, X12, X13, and X14 may have a different structure from the others.
In some implementations, A11 may be any one selected from R11 or X11, A12 may be any one selected from R12 or X12, A13 may be any one selected from R13 or X13, and A14 may be any one selected from R14 or X14. In some embodiments, the organometallic compound may be expressed as MR11X12X13B11 (MRX2B) or MR11R12X13B11 (MR2XB) In some other embodiments, the organometallic compound may be expressed as MR11X12X13X14 (MRX3), MR11R12X13X14 (MR2X2) or MR11R12R13X14 (MR3X). At this time, R may be a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group that are covalently bonded to the M including R11, R12, R13, and R14. X may be a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group that are covalently bonded to the M that includes X11, X12, X13 and X14 and at least one hetero atom.
In some implementations, B11 may include a ylide group including pyridinium of [C5H5NH]+, that is, a pyridinium ylide group. For example, B11 may be R31—C(═O)—N— ([C5H5NH]+)—*, R32—S(═O)2—N−([C5H5NH]+)—*, R33—C(═O)—C−([C5H5NH]+)—*, or [C5H5NH]+—O−—*. Wherein, * is a binding site with M, and R31, R32, and R33 may each be hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or a substituted or unsubstituted phenyl group.
In some implementations, B11 may be R34-Ht+(R35)(R36)—C−(R37)—*. Wherein * is a binding site with M, Ht is a hetero atom such as nitrogen (N), sulfur(S), or phosphorus (P), and R34, R35, R36, and R37 may each be hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or a substituted or unsubstituted phenyl group.
In some implementations, B11 may include an aromatic ring, a heteroaromatic ring, or any combination thereof at a terminal. The aromatic ring may be a single aromatic ring such as benzene; a heteroaryl group such as pyridine, pyrimidine, thiophene, etc.; or a condensed aryl group such as quinolone, isoquinoline, naphthalene, anthracene, and phenanthrene, etc., The heteroaryl group and the condensed aryl group may include at least one hetero atom selected from oxygen (O), sulfur(S), and nitrogen (N).
In some implementations, B11 may include a reactive group at a terminal. For example, the reactive group may include an acid group selected from a hydroxyl group, a sulfonate group, a carboxyl group, and a phosphonate group, but is not limited thereto.
In some implementations, B11 may include a sterically bulky functional group at the terminal. For example, B11 may include a sterically bulky functional group at the terminal like a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or a substituted or unsubstituted phenyl group, but is not limited thereto.
In some implementations, when B11 includes the above-described pyridinium ylide group, B11 may include a bulky functional group that binds to the pyridine of the pyridinium ylide group. Through combining B11 with the bulky functional group, a reaction in which the central metal reacts with moisture to form a hydroxy group (OH group) may be suppressed, thereby providing a more stable organometallic compound. Also, the bulky functional group may be separated from the organometallic compound through a decomposition reaction of the ylide ligand in an exposure process, thereby preventing critical dimension (CD) distribution deterioration of a pattern.
For example, B11 may include at least one structure selected from the following structures.
In the above structures, as described above, R31, R32, R33, R34, R35, R36, and R37 may each include hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or a substituted or unsubstituted phenyl group.
The first atom having a formal charge of −1 in B11 may have at least one binding site capable of binding to the central metal. In some embodiments, B111 may include a monodentate ligand. In some other embodiments, B11 may include a polydentate ligand. The polydentate ligand may be a bidentate ligand including two atoms capable of coordination, a tridentate ligand including three atoms capable of coordination, or a tetradentate ligand including four atoms capable of coordination, but is not limited thereto.
In some implementations, when B11 includes a pyridinium ylide group, B11 may be a bidentate ligand including an atom that is coordinately bonded to an ortho, meta, or para position of pyridinium included in the pyridinium ylide group. For example, B11 may be a bidentate ligand including pyridine or thiophene bonded to the ortho, meta, or para position of the pyridinium. In some other embodiments, B11 may be a tridentate ligand including an ester group.
For example, B11 may include at least one structure selected from the following structures.
In the above structures, R41, R42, R43, R44, R45, R46, R47, R48, R49, and R50 may each include hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or a substituted or unsubstituted phenyl group.
The organometallic compound may have a composition of M(A11)a(A12)b(A13)c(B11)d (MA3B) of Formula 1 or a composition of M(A11)a(A12)b (A13)c(A14)d (MA4) of Formula 2, but it is not limited thereto, and may have a composition of M(A11)a(A12)b(B11)c(B12)d (MA2B2), M(A11)a(B11)b(B12)c(B13)d (MAB3), or M(B11)a(B12)b(B13)c(B14)d (MB4). At this time, A may be a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group that covalently or coordinately bonded to M including A11, A12, A13, and A14, and B may be a C1 to C30 aliphatic hydrocarbon group including a first atom with a formal charge of −1 that coordinates with the M including B11, B12, B13, and B14 and a second atom that is a heteroatom with a formal charge of +1 bonded to the first atom with a formal charge of −1 or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group including the first atom and the second atom, that is, the above-mentioned ylide group. a, b, c, and d are each independently integers greater than 0 and less than or equal to 4, and a+b+c+d is less than or equal to 4.
In some implementations, among a total weight of the photoresist composition, a content of the organometallic compound may be in a range from about 0.1 wt % to about 20 wt %. In some embodiments, the content of the organometallic compound may be in a range from about 0.1 wt % to about 15 wt %, from about 0.1 wt % to about 10 wt %, or from about 0.1 wt % to about 5 wt %. If the content of the organometallic compound is excessively high, there is a risk that pattern stability may deteriorate due to crosslinking reaction being concentrated on an exposed surface. Conversely, if the content of the organometallic compound is excessively low, the organometallic compound may not form a sufficient amount of reactive groups and/or radicals, which may reduce pattern precision.
In the photoresist composition according to some implementations, the central metal may be included in an amount of about 0.1 wt % to about 5 wt % based on the total weight of the photoresist composition, but is limited thereto.
The organometallic compound included in the photoresist composition according to the embodiments may be obtained by purchasing a commercially available product or by synthesizing it from a well-known precursor using a method known to those skilled in the art.
In some implementations, the photoresist composition according an embodiment may further include an organic ligand precursor. The organic ligand precursor may have a structure capable of forming a coordination complex with the central metal. That is, the organic ligand precursor may have a structure in which there is at least one binding site with the central metal.
The organic ligand precursor may include a C1 to C30 aliphatic hydrocarbon group including a first atom with a formal charge of −1 that may provide a binding site to the central metal and a second atom that is a hetero atom with a formal charge of +1 bonded to the first atom or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group including the first atom and the second atom, that is, the ylide group described above.
In other words, the organic ligand precursor may be a compound that exists independently by being stabilized through resonance and delocalization in a state that the ylide group is separated from the central metal, rather than in a state that the ylide group is bonded to the central metal, such as B11, B12, B13, and B14.
In example embodiments, the organic ligand precursor may include R51—C(═O)—N—([C5H5NH]+), R52—S(═O)2—N—([C5H5NH]+), R53—C(═O)—C— ([C5H5NH]+), or [C5H5NH]+—O−. Wherein R51, R52, and R53 may each be hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or a substituted or unsubstituted phenyl group.
In some implementations, the organic ligand precursor may include R54-Ht+(R55) (R56)—C—(R57). Wherein Ht may be a hetero atom such as nitrogen (N), sulfur(S), or phosphorus (P), and R54, R55, R56, and R57 may each be hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or a substituted or unsubstituted phenyl group.
The organic ligand precursor may form a coordination complex by binding to the central metal through a ligand substitution reaction with the ligand bonded to the central metal. For example, in an organometallic compound including A11, A12, A13, and/or A14, the organic ligand precursor may form an organometallic compound including B11, B12, B13, and/or B14 through a ligand substitution reaction with A11, A12, A13, and/or A14
In the photoresist composition according to some implementations, a molar ratio of the organic ligand precursor to the organometallic compound may be in a range from about 0.01 to about 10, but is not limited thereto.
In some implementations, the photoresist composition may further include a photoinitiator. The photoinitiator may be configured to generate an acid or radical by absorbing first light. The photoinitiator may generate an acid or radical by absorbing the first light in an exposed region of the photoresist film after the photoresist film obtained from the photoresist composition is exposed to the first light. The acid or radical generated from the photoinitiator may react with the organic ligand of the organometallic compound and induce a dissociation reaction of the organic ligand. Accordingly, when the photoinitiator is included in the photoresist composition according to some implementations, the desorption of the organic ligand from the organometallic compound may occur by the acid or radical generated from the photoinitiator, and a cross-linking reaction between adjacent molecules may occur during a bake process.
When the photoinitiator is included in the photoresist composition according to the embodiments, the photoinitiator may compensate for the relatively low reactivity of the organometallic compound when the photoresist film obtained from the photoresist composition is exposed to light, and In addition, the sensitivity to light in the exposed region of the photoresist film may be adjusted depending on the content of the photoinitiator. In particular, in the exposed region of the photoresist film, the photoinitiator may induce a photoreaction limited to the exposed region of the photoresist film by promoting a ligand dissociation reaction in the organometallic compound using an acid or radical.
The photoinitiator may include a photoacid generator (PAG) configured to generate acid by exposure, a photoradical generator (PRG) configured to generate radicals by exposure, or any combination of the PAG and the PRG.
The PAG may generate acid when exposed to any light selected from a KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), and EUV laser (13.5 nm). In example embodiments, the PAG may include triarylsulfonium salts, diaryliodonium salts, sulfonates, or a mixture thereof. For example, the PAG may include, triphenylsulfonium triflate, triphenylsulfonium antimonate, diphenyliodonium triflate, diphenyliodonium antimonate, methoxydiphenyliodonium triflate, di-t-butyldiphenyliodonium triflate), 2,6-dinitrobenzyl sulfonates, pyrogallol tris(alkylsulfonates)), N-hydroxysuccinimide triflate, norbornene-dicarboximide-triflate, triphenylsulfonium nonaflate, diphenyliodonium nonaflate, methoxydiphenyliodonium nonaflate, di-t-butyldiphenyliodonium nonaflate, N-hydroxysuccinimide nonaflate, norbornene-dicarboximide-nonaflate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate (PFOS), diphenyliodonium PFOS, methoxydiphenyliodonium PFOS, di-t-butyldiphenyliodonium triflate, N-hydroxysuccinimide PFOS, norbornene-dicarboximide PFOS, or any combination thereof, but is not limited thereto.
When the PRG is exposed to any light selected from a KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), and EUV laser (13.5 nm), the PRG absorbs the light and generates radicals, and thus, polymerization of an organometallic compound included in the photoresist composition according to the embodiments may be initiated. In some implementations, the PRG may include an acylphosphine oxide-based compound, an oxime ester-based compound, etc.
Examples of the acylphosphine oxide-based compounds may include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, etc.
Examples of the oxime ester-based compound may include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl) oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl) oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl) oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl) oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl) oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl) oxime, [9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolane-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl) oxime, etc.
In some implementations, commercially available products (BASF product, brand name) such as IRGACURE 651, IRGACURE 184, IRGACURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE TPO, IRGACURE 819, IRGACURE OXE01, IRGACURE OXE02, IRGACURE MBF, IRGACURE 754 may be used as the PRG.
The resist composition, according to some implementations, may not include the photoinitiator, may include only a single material selected from the PAG and the PRG as the photoinitiator, or may include at least two substances selected from the PAG and the PRG. When the photoinitiator is included in the photoresist composition according to the embodiments, the photoinitiator may be included in an amount in a range from about 0.02 wt % to about 10 wt % based on the total amount of the organometallic compound, but is not limited thereto.
A solvent included in the photoresist composition may include an organic solvent. The organic solvent may include at least one of ether, alcohol, glycol ether, aromatic hydrocarbon compound, ketone, and ester, but is not limited thereto. For example, the organic solvent may include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether, propylene glycol butyl ether acetate, ethanol, propanol, isopropyl alcohol, isobutyl alcohol, 4-methyl-2-pentanol (methyl isobutyl carbon (MIBC)), hexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol, propylene glycol, heptanone, Propylene carbonate, butylene carbonate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetic acid, ethyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, gamma-butyrolactone, methyl-2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxy propionate, ethoxyethoxy propionate, or any combination thereof.
In the photoresist composition, according to some implementations, the solvent may be included in a remaining amount excluding the contents of the main components including the organometallic compound and a photosensitive additive. In some implementations, the solvent may be included in an amount in a range from about 70 wt % to about 99.8 wt % based on the total weight of the photoresist composition, but is not limited thereto.
In some implementations, when the photoresist composition according to the embodiments includes the PAG as the photoinitiator, the photoresist composition may further include a basic quencher. The basic quencher may include a compound capable of trapping acids in the non-exposed region when acids generated from the PAG included in the photoresist composition according to the embodiments or acids generated from other photodegradable compounds diffuse into the non-exposed region. Because the basic quencher is included in the photoresist composition according to some implementations, the diffusion rate of acid in the photoresist film obtained from the photoresist composition may be suppressed.
In some implementations, the basic quencher may include a primary aliphatic amine, a secondary aliphatic amine, a tertiary aliphatic amine, an aromatic amine, an amine including a heteroaromatic ring, a nitrogen-including compound having a carboxyl group, a nitrogen-including compound having a sulfonyl group, a nitrogen-including compound having a hydroxyl group, a nitrogen-including compound having a hydroxyphenyl group, an alcoholic nitrogen-including compound, amides, imides, carbamates, or ammonium salts. For example, the basic quencher may include triethanol amine, triethyl amine, tributyl amine, tripropyl amine, hexamethyl disilazan, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, N,N-bis(hydroxyethyl) aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, dimethylaniline, 2,6-diisopropylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, or any combination thereof, but is not limited to the examples above.
In some implementations, the basic quencher may include a photobase generator. The photobase generator may generate a base by absorbing active energy rays through light irradiation and decomposing its chemical structure. Accordingly, when a partial region of a photoresist film formed from a photoresist composition including a basic quencher including a photobase generator is exposed, the photobase generator traps acid in the exposed region of the photoresist film, and thus, the sensitivity in the exposure region may be adjusted and the diffusion of acid from the exposed region to the non-exposed region may be suppressed. Accordingly, a metal structure network consisting of a metal oxide including the central metal may be formed selectively only in the exposed region of the photoresist film, and thus, an adverse effect due to undesired diffusion of the acid, for example, the problem such as deterioration of critical dimension (CD) distribution at edges of the photoresist pattern obtained after a development process may be prevented.
A material constituting the photobase generator is not particularly limited as long as it generates a base by light irradiation. In some implementations, the photobase generator may be comprised of a non-ionic photobase generator. In some implementations, the photobase generator may include an ionic photobase generator.
In some implementations, the photobase generator may include a carboxylate or sulfonate salt of a photodecomposable cation. For example, the photodecomposable cation included in the photobase generator may be a sulfonium cation. The sulfonium cation may include a substituted or unsubstituted C1 to C12 alkyl group, a substituted or unsubstituted C3 to C12 cycloalkyl group, a C6 to C30 aryl group, or a C2 to C30 heteroaryl group. The alkyl group, the cycloalkyl group, the aryl group, and the heteroaryl group may include at least one hetero atom selected from O atoms, S atoms, and N atoms. For example, the sulfonium cation may include, but is limited to, a phenyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, or an isopropyl group.
The photodecomposable cation included in the photobase generator may form a complex with an anion of C1 to C20 carboxylic acid. The carboxylic acid may be, for example, formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, or salicylic acid, but is not limited thereto.
In some implementations, triphenylsulfonium heptafluorobutyric acid, or triphenyl sulfonium hexafluoroantimonate (TPS-SbF6) may be used as the photobase generator, but it is not limited thereto.
In the photoresist composition, according to some implementations, the basic quencher may be used alone, or a mixture of two or more types of radical quenchers may be used. The basic quencher may be included in a molar ratio range from about 0.01 to about 0.5 based on the total content of the organometallic compound, but is not limited thereto.
In some implementations, when the PRG is included as the photoinitiator in the photoresist composition, the photoresist composition may further include a radical quencher capable of trapping radicals.
In some implementations, the radical quencher may include a quinone type free radical, or a nitroxide (IUPAC name: aminoxyl) free radical.
The quinone type free radical may include p-benzoquinone, 1,4-dihydroxybenzene, 4-methoxyphenol, hydroquinone monomethyl ether, hydroquinone monophenyl ether, mono-t-butyl hydroquinone (MTBHQ), di-t-butyl hydroquinone, di-t-amyl hydroquinone, toluhydroquinone, p-benzoquinone dioxime, 2,6-dichloro-1,4-benzoquinone, 2,3,5,6-tetramethyl-1,4-benzoquinone, 2,5-dichloro-3,6-dihydroxy-p-benzoquinone, methyl-p-benzoquinone, 6-anilinoquinoline-5,8-quinone, pyrroloquinoline quinone, 2-allyl-6-methoxybenzo-1,4-quinone, or any combination thereof, but is not limited thereto.
The nitroxide free radicals may include di-tert-butyl nitroxide (DTBN), 2,2,6,6-tetramethyl-1-peperidine 1-oxyl (TEMPO), 4-oxo-2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl(oxo TEMPO), 1,1,3,3-tetraethylisoindolin-N-oxyl, N-tert-butyl-N-[1-(diethoxyphosphoryl)-2,2-dimethylpropyl]aminoxyl (SGI), N-tert-butyl-N-(2-methyl-1-phenylpropyl)aminoxyl (TIPNO), or combinations thereof, but are not limited thereto.
When performing a photolithography process using a photoresist composition, according to some implementations, radicals generated from the PRG are quenched by the radical quencher in the exposed region of the photoresist film obtained from the photoresist composition, and thus, the sensitivity adjustment in the exposed region may be possible, and radicals flowing from the exposed region to the non-exposed region may be quenched by the radical quencher. Accordingly, a network consisting of a metal oxide that selectively includes the central metal in the exposed region may be formed, and adverse effects due to unwanted diffusion of the radicals, for example, problems such as the deterioration of CD distribution at edges of the photoresist pattern obtained after a development process may be prevented.
In the photoresist composition, according to some implementations, the radical quencher may be used alone, or a mixture of two or more types of radical quenchers may be used. The radical quencher may be included in a molar ratio range from about 0.01 to about 0.5 based on the total content of the organometallic compound, but is not limited thereto.
In some implementations, the photoresist composition may further include at least one selected from a leveling agent, a surfactant, a dispersant, a moisture absorbent, and a coupling agent.
The leveling agent improves coating flatness when coating the photoresist composition on a substrate, and a known leveling agent commercially available may be used.
The surfactant may improve coating uniformity and wettability of the photoresist composition. In example embodiments, the surfactant may include a sulfuric acid ester salt, a sulfonate salt, a phosphoric acid ester, soap, an amine salt, a quaternary ammonium salt, polyethylene glycol, an alkylphenolethylene oxide adduct, a polyhydric alcohol, a nitrogen-including vinyl polymer, or any combination thereof, but is not limited thereto. For example, the surfactant may include alkylbenzenesulfonate, alkylpyridinium salt, polyethylene glycol, or quaternary ammonium salt. When the photoresist composition includes the surfactant, the surfactant may be included in an amount range from about 0.001 wt % to about 3 wt % based on the total weight of the photoresist composition.
The dispersing agent may ensure that each component constituting the photoresist composition is uniformly dispersed within the photoresist composition. In some implementations, the dispersant may include epoxy resin, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, glucose, sodium dodecyl sulfate, sodium citrate, oleic acid, linoleic acid, or any combination thereof, but is not limited thereto. When the photoresist composition includes the dispersant, the dispersant may be included in an amount range from about 0.001 wt % to about 5 wt % based on the total weight of the photoresist composition.
The moisture absorbent may prevent adverse effects caused by moisture in the photoresist composition. In some implementations, the moisture absorbent may include polyoxyethylene nonylphenolether, polyethylene glycol, polypropylene glycol, polyacrylamide, or any combination thereof, but is not limited thereto. When the photoresist composition includes the moisture absorbent, the moisture absorbent may be included in an amount range from about 0.001 wt % to about 10 wt % based on the total weight of the photoresist composition.
The coupling agent may improve adhesion to a lower film when coating the photoresist composition on the lower film. In some implementations, the coupling agent may include a silane coupling agent. The silane coupling agent may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl trichlorosilane, vinyltris(β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, or trimethoxy [3-(phenylamino) propyl]silane, but is not limited thereto. When the photoresist composition includes the coupling agent, the coupling agent may be included in an amount range from about 0.001 wt % to about 5 wt % based on the total weight of the photoresist composition.
When a photoresist film obtained from a photoresist composition including the organometallic compound, according to some implementations, is exposed to light, the organometallic compound may absorb the light, and some of organic ligands in the organometallic compound may break bonds with the central metal and may dissociate. For example, when the organometallic compound is exposed to any one light selected from a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), and an EUV laser (13.5 nm), the organometallic compound may absorb the light, and some of the organic ligands may break bonds with the central metal and dissociate.
In some implementations, when a photoresist film obtained from a photoresist composition including an organometallic compound according to example embodiments is exposed to light, the ylide ligand may decompose.
Specifically, due to the exposure of the photoresist film, secondary electrons may be generated, and due to the secondary electrons, the bond between the first atom with a −1 formal charge and the second atom with a +1 formal charge of the ylide ligand is broken, and the second atom and the secondary electron may combine. As a result, a functional group including the second atom of the ylide ligand may be separated from the organometallic compound.
Alternatively, radicals may be generated by the photoinitiator included in the photoresist composition, and due to the breakage of bonds of other organic ligands around the ylide ligand with the central metal, the radicals may be ligand radicals having unpaired electrons. The bond between the first atom with a formal charge of −1 and the second atom with a formal charge of +1 of the ylide ligand is decomposed by the radical generated by the photoinitiator or the ligand radical, and a functional group including the second atom, which is desorbed by the decomposition of the bond between the first atom and the second atom, may combine with the radical generated by the photoinitiator or the ligand radical.
Accordingly, the first atom of the ylide ligand may be a radical having an unpaired electron. Thereafter, the first atom of the ylide ligand in a radical state may break the hydrogen bond with other surrounding atoms that have a lower bonding force than the bonding force between the first atom of the ylide ligand and hydrogen, and may bond with hydrogen. For example, the other surrounding atom having a bonding strength less than a bonding strength between the first atom of the ylide ligand and hydrogen may be an atom included in an alkyl group of another organic ligand surrounding the ylide ligand. Through the bond between the first atom of the ylide ligand and hydrogen, the coordination bond between the first atom of the ylide ligand and the central metal may be weakened, and thus, the desorption of the first atom of the ylide ligand from the central metal may easily occur. After the exposure process of the photoresist film, a desorption reaction of the first atom of the ylide ligand may be induced by a subsequent bake process, and as a result, the coordination bond between the first atom of the ylide ligand and the central metal may be weakened, and thus, the desorption reaction of the first atom may occur relatively easily.
Thereafter, a hydroxyl (OH) functional group may be generated at the site where the first atom of the ylide ligand is desorbed. A condensation reaction of the hydroxyl (OH) functional group may be induced by the baking process, and a cross-linking structure including a plurality of metals (M), for example, a M-O-M cross-linked structures may be formed through a cross-linking reaction of organic ligands of adjacent organometallic compounds. In present disclosure, the cross-linked structure may be referred to as a metal structure network.
For example, when a photoresist film obtained from a photoresist composition including the organometallic compound including the above-described formula 1 is exposed, B11 may be decomposed. The decomposition reaction of B11 may be expressed in Reaction Formula 1 or Reaction Formula 2 below. The Reaction Formula 1 or Reaction Formula 2 below shows the decomposition reaction when B11 is the above-described R31—C(═O)—N−([C5H5NH]+)—*.
In Reaction Formula 1 and Reaction Formula 2, X may be a photoinitiator, for example, may be a material having an X—H bond weaker than an N—H bond. For example, X may include carbon (C), silicon (Si), sulfur(S), or phosphorus (P) of a C1 to C20 alkyl group.
In some implementations, in a process in which the first atom of the ylide ligand in a radical state breaks a hydrogen bond with other surrounding atoms having a less bonding force than the bonding force between the first atom of the ylide ligand and hydrogen and forms a bond with the desorbed hydrogen, other atoms in the surrounding region may become radicals. Thereafter, the other atoms in the radical state may cause a chain reaction, that is, a chain reaction of decomposition of the ylide ligand. For example, the other atoms in the radical state may break the bond between the first atom of the ylide ligand and the second atom, and bond with the second atom of the ylide ligand. As a result, the first atom of the ylide ligand may become a radical with an unpaired electron, and other surrounding atoms again may become radicals, and thus, the above-described chain reaction of decomposition of the ylide ligand may occur again.
For example, when a photoresist film obtained from a photoresist composition including an organometallic compound having the above-described Formula 1 is exposed to light, B11 is decomposed, and a chain decomposition reaction may occur due to the radicals (in other words, the first atom in a radical state that occurs when the bond between the first atom of B11 with a formal charge of −1 and the second atom with a formal charge of +1 is broken) generated when B11 is decomposed. The chain reaction caused by the radical may be expressed in Reaction Formula 3 below. Reaction Formula 3 below shows a chain decomposition reaction when B11 is the above-described R31—C(═O)—N−([C5H5NH]+)—*.
In Reaction Formula 3, X may be a photoinitiator, for example, and may be a material having a X—H bond weaker than N—H bond. For example, X may include carbon (C), silicon (Si), sulfur(S), or phosphorus (P) of a C1 to C20 alkyl group.
The photoresist composition, according to some implementations, may include an organic ligand including an ylide group and constituting an organometallic compound by bonding with a central metal or an organic ligand precursor including an ylide group capable of forming a coordination complex with the central metal. In the exposure process, because a chain decomposition reaction is induced by using a decomposition reaction of the ylide ligand and radicals generated by the decomposition reaction, during storage and/or transportation of the photoresist composition or during a process of manufacturing an integrated circuit device that uses the photoresist composition, unwanted changes over time caused by light or moisture in the air may be prevented, and accordingly, by suppressing a reaction in which the central metal reacts with moisture to generate a hydroxy group (OH group), the temporal stability of the photoresist composition may be secured, and the process stability of manufacturing an integrated circuit device that uses the photoresist composition may be secured.
In addition, due to the high reactivity and short lifespan of the radical generated by the decomposition of the ylide ligand, the decomposition reaction of other ylide ligands in the non-exposed area, which may occur when the radical generated by the decomposition of the ylide ligand penetrates into the non-exposed region, may be relatively low, and thus, the exposure sensitivity in the exposed region of the photoresist film may be increased. Accordingly, high resolution and improved sensitivity may be provided in the photolithography process, and the dimensional precision of a pattern to be formed may be improved by preventing CD distribution deterioration of the pattern obtained by the photolithography process.
Hereinafter, a method of manufacturing an integrated circuit device using a photoresist composition according to embodiments is described using specific examples.
In
The substrate 100 may include a semiconductor substrate. The feature layer 110 may include an insulating film, a conductive film, or a semiconductor film. For example, the feature layer 110 may include a metal, an alloy, metal carbide, metal nitride, metal oxynitride, metal oxycarbide, semiconductor, polysilicon, oxide, nitride, oxynitride, or any combination thereof, but is not limited thereto.
In some implementations, as illustrated in
To form the photoresist film 130, the photoresist composition, according to some implementations, may be coated on the lower film 120 and then heat treated. The coating may be performed by methods such as spin coating, spray coating, dip coating, etc. The process of heat treating the photoresist composition may be performed at a temperature in a range from about 80° C. to about 300° C. for about 10 seconds to about 100 seconds, but is not limited thereto. A thickness of the photoresist film 130 may be tens to hundreds of times the thickness of the lower film 120. The photoresist film 130 may be formed to have a thickness in a range from about 10 nm to about 1 μm, but is not limited thereto.
In some implementations, the photoresist composition for forming the photoresist film 130 includes an organometallic compound, and the organometallic compound may include a central metal and an ylide ligand coordinated with the central metal.
In some implementations, when the photoresist composition for forming the photoresist film 130 further includes an ylide ligand precursor, after the photoresist film 130 is formed or during the photoresist film 130 is formed, a modified organometallic compound may be formed by binding the ylide ligand to the central metal of the organometallic compound through a ligand substitution reaction between the organometallic compound and the ylide ligand precursor in the photoresist film 130.
In
Specifically, when the first region 132, which is a part of the photoresist film 130, is exposed according to process P30 of
Therefore, after the photoresist film 130 is formed, an undesired reaction due to light or moisture in the photoresist film 130, for example, a reaction in which the central metals included in the photoresist film 130 react with moisture to generate a hydroxy group (OH group) may be suppressed until the subsequent exposure process is performed, thereby ensuring the stability of the photoresist composition over time.
In addition, due to the high reactivity and short lifespan of the radical generated by the decomposition of the ylide ligand, the decomposition reaction of other ylide ligands in the non-exposed area, which may occur when the radical generated by the decomposition of the ylide ligand penetrates into the non-exposed region, may be relatively low, and thus, the exposure sensitivity in the exposed region of the photoresist film may be increased. Accordingly, high resolution and improved sensitivity may be provided in the photolithography process, and the dimensional precision of a pattern to be formed may be improved by preventing CD distribution deterioration of the pattern obtained by the photolithography process.
In some implementations, when the photoresist film 130 includes a photoinitiator, when the first region 132, which is a part of the photoresist film 130, is exposed according to process P30 of
In some implementations, to expose the first region 132 of the photoresist film 130, a photomask 140 having a plurality of light shielding areas LS and a plurality of light transmitting areas LT is aligned at a predetermined position on the photoresist film 130, and the first region 132 of the photoresist film 130 may be exposed through the plurality of light transmitting areas LT of the photomask 140. To expose the first region 132 of the photoresist film 130, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), a F2 excimer laser (157 nm), or an EUV laser (13.5 nm) may be used.
In some implementations, the photomask 140 may include a transparent substrate 142 and a plurality of light blocking patterns 144 formed in the plurality of light blocking areas LS on the transparent substrate 142. The transparent substrate 142 may include quartz. The plurality of light blocking patterns 144 may include chrome (Cr). The plurality of light transmitting areas LT may be defined by the plurality of light blocking patterns 144. According to the present inventive concept, to expose the first region 132 of the photoresist film 130, a reflective photomask (not shown) for EUV exposure may be used instead of the photomask 140.
In
The bake process may be performed at a temperature in a range from about 50° C. to about 400° C. for about 10 seconds to about 150 seconds. For example, the bake process may be performed at a temperature in a range from about 150° C. to about 250° C. for about 60 seconds to about 120 seconds, but is not limited thereto.
In some implementations, in the first region 132, because the bond between the central metal and the first atom having a formal charge of −1 of the ylide ligand is weakened through a decomposition reaction of the ylide ligand, while performing the bake process of the photoresist film 130, the bond between the central metal and the first atom of the ylide ligand may be relatively easily broken. Accordingly, the first atom of the ylide ligand may be desorbed from the central metal, and a condensation reaction of the hydroxyl (OH) functional group is induced at the site where the first atom of the ylide ligand is desorbed, thus, a dense metal structure network may be formed.
In some implementations, when the photoresist film 130 includes a photoinitiator, while performing the bake process of the photoresist film 130, in the first region 132, a desorption reaction of the organic ligand may be induced in the organometallic compound using an acid or a radical generated from the photoinitiator, and a condensation reaction of the hydroxyl (OH) functional group generated at the site where the organic ligand is desorbed is induced, and thus, a dense metal structure network may be formed.
On the other hand, a metal structure network is not formed in the second region 134, which is a non-exposed region of the photoresist film 130, and accordingly, the difference in solubility in a developer between the first region 132 and the second region 134 of the photoresist film 130 may increase.
In
The photoresist pattern 130P may include a plurality of openings OP. After the photoresist pattern 130P is formed, a lower pattern 120P may be formed by removing portions of the lower film 120 exposed through the plurality of openings OP.
In some implementations, the development of the photoresist film 130 may be performed using a negative-tone development (NTD) process.
In some implementations, a developer including an organic solvent may be used to develop the photoresist film 130. For example, the developer may include ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, etc.; alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, etc.; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, etc.; aromatic compounds such as benzene, xylene, toluene, etc.; or any combination thereof, but is not limited thereto.
As explained with reference to
In some implementations, after forming the photoresist pattern 130P by developing the photoresist film 130, a process of hard bake the obtained resultant product may further be performed. Through the hard bake process, unnecessary substances such as developer remaining on the resultant product on which the photoresist pattern 130P is formed may be removed. In addition, while performing the bake process according to process P40 of
The hard bake process may be performed at a temperature in a range from about 50° C. to about 400° C. for about 10 seconds to about 150 seconds. For example, the hard bake process may be performed at a temperature in a range from about 150° C. to about 250° C. for about 60 seconds to about 120 seconds, but is not limited thereto.
In
In order to process the feature layer 110, various processes, such as a process of etching the feature layer 110 exposed through the opening OP of the photoresist pattern 130P, a process of implanting impurity ions into the feature layer 110, a process of forming an additional film on the feature layer 110 through the opening (OP), and a process of deforming a part of the feature layer 110 through the opening (OP), etc. In
In some implementations, in the process described with reference to
In
According to the manufacturing method of an integrated circuit device according to the present disclosure described with reference to
While this disclosure contains many specific implementation details, these should not be construed as limitations on the scope of what may be claimed. Certain features that are described in this disclosure in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations, one or more features from a combination can in some cases be excised from the combination, and the combination may be directed to a subcombination or variation of a subcombination.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0161441 | Nov 2023 | KR | national |
