Area selective atomic layer deposition method, apparatus therefor, and HZO material film structure manufactured thereby

Abstract

An area selective atomic layer deposition method is provided. The area-selective atomic layer deposition method includes the steps of: preparing a substrate including a first area containing a metal layer, and a second area excluding the first area; providing oxygen gas to the substrate to activate the metal layer of the first area; and supplying a first precursor containing hafnium (Hf), a second precursor containing zirconium (Zr), and a reactant to the substrate to selectively deposit a HZO(Hf1-xZrxO2, x>0) material film on the metal layer of the first region among the first region and the second region.

Description

Area-selective atomic layer deposition method, device therefor, and HZO material film structure manufactured thereby

[0001] The present invention relates to a region-selective atomic layer deposition method, a device therefor, and a HZO material film structure manufactured thereby.

[0002] Conventional area-selective atomic layer deposition (AS-ALD) has been primarily studied by suppressing thin-film growth in localized areas by forming a monolayer of surface inhibitor (primarily utilizing a self-assembled monolayer (SAM)) in non-growth areas where growth is not desired. However, AS-ALD processes utilizing SAMs have several limitations, such as various issues in the SAM adsorption process and lack of compatibility with three-dimensional structures. Therefore, a process that can improve these limitations is required.

[0003] Specifically, the AS-ALD process based on the solution-based SAM surface modification process has not been able to avoid issues such as a long adsorption time of the single-layer inhibitor material formed on the surface, a reduction in selectivity due to non-uniform formation within the three-dimensional structure, and a reduction in feature size (mushroom effect) when applied to a pattern structure at the level of several tens of nm, and therefore has not been applied to the formation of ultra-fine patterns for actual semiconductor processes. Although vapor-phase SAM adsorption research is being conducted on a very limited number of SAM materials, as described above, the introduction of the AS-ALD process is at a standstill due to limitations such as a reduction in selectivity due to non-uniform coating when applied to a three-dimensional structure and the ingress of impurities into the thin film. Therefore, there is a need for an AS-ALD process technology that is compatible with the production of three-dimensional memory devices, breaking away from the conventional SAM-based localized inactivation AS-ALD process.

[0004] The technical problem to be solved by the present invention is to provide a region-selective atomic layer deposition method, a device therefor, and a HZO material film structure manufactured through the method.

[0005] Another technical problem to be solved by the present invention is to provide a method for selectively depositing a HZO material film on a desired area.

[0006] Another technical problem to be solved by the present invention is to provide a method for selectively depositing a HZO material film without using an inhibitor.

[0007] Another technical problem that the present invention seeks to solve is to provide a HZO material film from which impurities such as carbon are removed.

[0008] Another technical problem to be solved by the present invention is to provide a HZO material film crystallized in a tetragonal phase.

[0009] Another technical problem to be solved by the present invention is to provide an HZO material film exhibiting anti-ferroelectric properties.

[0010] Another technical problem that the present invention seeks to solve is to provide a HZO material film having a high dielectric constant value.

[0011] Another technical problem that the present invention seeks to solve is to provide an HZO material film having stable leakage current characteristics.

[0012] The technical problems to be solved by the present invention are not limited to those described above.

[0013] To solve the above-described technical problems, the present invention provides a region-selective atomic layer deposition method.

[0014] According to one embodiment, the region-selective atomic layer deposition method comprises the steps of preparing a substrate including a first region including a metal layer and a second region excluding the first region, providing oxygen gas on the substrate to activate the metal layer in the first region, and providing a first precursor including hafnium (Hf), a second precursor including zirconium (Zr), and a reactant on the substrate to deposit HZO(Hf) on the metal layer in the first region among the first region and the second region. 1-x Zr x O2, x>0) may include a step of selectively depositing a material film.

[0015] According to one embodiment, in the step of activating the metal layer of the first region, the oxygen molecules of the oxygen gas are dissociatively chemisorbed onto the surface of the metal layer by the surface catalytic action of the metal layer, and the metal layer is activated as oxygen atoms are adsorbed onto the surface of the metal layer.

[0016] According to one embodiment, the first precursor and the second precursor may comprise a cyclopentadienyl ligand.

[0017] In one embodiment, the first precursor may comprise cyclopentadienyl-tris(dimethylamino)-hafnium, and the second precursor may comprise cyclopentadienyl-tris(dimethylamino)-zirconium.

[0018] In one embodiment, the reactant may include oxygen (O2).

[0019] According to one embodiment, the region-selective atomic layer deposition method may further include, after the step of selectively depositing an HZO material film on the metal layer of the first region, a step of treating the HZO material film with ozone (O3) to remove carbon (C) within the HZO material film.

[0020] According to one embodiment, the region-selective atomic layer deposition method may further include, after the step of selectively depositing an HZO material film on the metal layer of the first region, a step of heat-treating the HZO material film to crystallize the HZO material film into a tetragonal phase.

[0021] According to one embodiment, as the HZO material film is crystallized in a tetragonal phase, the HZO material film may exhibit anti-ferroelectric properties.

[0022] According to one embodiment, the step of selectively depositing a HZO material film on the metal layer of the first region may include the step of providing the first precursor and the reactant on the substrate to form a first material film including HfO2 reacted with the first precursor and the reactant, and the step of providing the second precursor and the reactant on the first material film to form a second material film including ZrO2 reacted with the second precursor and the reactant.

[0023] According to one embodiment, the reaction of the first precursor and the reactant and the reaction of the second precursor and the reactant may occur on the activated metal layer, so that the first material film and the second material film may be formed on the activated metal layer.

[0024]

[0025] To solve the above-described technical problems, the present invention provides a region-selective atomic layer deposition device.

[0026] According to one embodiment, the region-selective atomic layer deposition device comprises a chamber in which a substrate is placed, a first region including a metal layer, and a second region excluding the second region, an oxygen gas supply unit that supplies oxygen gas into the chamber to activate the metal layer of the first region, a precursor supply unit that supplies a first precursor including hafnium (Hf) and a second precursor including zirconium (Zr) into the chamber, and a reactant supply unit that provides a reactant to react with the first precursor and the second precursor into the chamber, wherein HZO(Hf) is deposited on the metal layer of the first region among the first region and the second region. 1-x Zr x O2, x>0) may include selectively depositing a material film.

[0027] In one embodiment, the first precursor, the second precursor, and the reactant provided into the chamber may be included to react only on the activated metal layer.

[0028]

[0029] To solve the above-described technical problems, the present invention provides a HZO material film structure.

[0030] According to one embodiment, the HZO material film structure comprises a substrate including a first region including a metal layer and a second region excluding the first region, and HZO (Hf) formed on the metal layer of the first region 1-x Zr x O2, x>0) material film, wherein the HZO material film is crystallized in a tetragonal phase and may include anti-ferroelectric properties.

[0031] According to one embodiment, the metal layer comprises titanium nitride (TiN), ruthenium (Ru), platinum (Pt), tantalum nitride (TaN), ruthenium oxide (RuO2), tungsten (W), or tungsten nitride (WN). x , x>0), molybdenum (Mo), and molybdenum nitride (MoN x , x>0) can contain any one of them.

[0032] A region-selective atomic layer deposition method according to an embodiment of the present invention comprises the steps of: preparing a substrate including a first region including a metal layer and a second region excluding the first region; providing oxygen gas on the substrate to activate the metal layer in the first region; and providing a first precursor including hafnium (Hf), a second precursor including zirconium (Zr), and a reactant on the substrate to deposit HZO(Hf) on the metal layer in the first region among the first region and the second region. 1-x Zr x A step of selectively depositing a material film (O2, x>0) may be included. Accordingly, the HZO material film can be selectively deposited on a specific region without using an inhibitor.

[0033] In addition, after the HZO material film is selectively deposited on the metal layer of the first region, the HZO material film can be ozone treated and heat treated. Accordingly, impurities (carbon, etc.) in the HZO material film are removed and crystallized into a tetragonal phase, so that the HZO material film can have a high dielectric constant value, exhibit anti-ferroelectric characteristics, and exhibit stable leakage current characteristics.

[0034] FIG. 1 is a flowchart illustrating a region-selective atomic layer deposition method according to an embodiment of the present invention.

[0035] FIG. 2 is a drawing for explaining step S100 of the region-selective atomic layer deposition method according to an embodiment of the present invention.

[0036] FIG. 3 is a drawing for explaining step S200 of the region-selective atomic layer deposition method according to an embodiment of the present invention.

[0037] FIG. 4 and FIG. 5 are drawings for explaining step S300 of the region-selective atomic layer deposition method according to an embodiment of the present invention.

[0038] FIG. 6 is a drawing for explaining the precursor volume used in step S300 of the area-selective atomic layer deposition method according to an embodiment of the present invention.

[0039] FIG. 7 is a drawing for explaining a gapfill process using an area-selective atomic layer deposition method according to an embodiment of the present invention.

[0040] FIGS. 8 to 10 are drawings for explaining a process in which a region-selective atomic layer deposition method according to an embodiment of the present invention is applied to a capacitor having a filler-type lower electrode.

[0041] FIGS. 11 to 13 are drawings for explaining a process in which a region-selective atomic layer deposition method according to an embodiment of the present invention is applied to a capacitor having a lower electrode of a silicide type.

[0042] Figure 14 is a drawing for explaining the combination of precursors and reactants for forming a HZO material film using atomic layer deposition.

[0043] Figure 15 is a drawing for explaining the combination of a reactant material and a substrate material for forming a HZO material film using an atomic layer deposition method.

[0044] Fig. 16 is a drawing for explaining the XPS analysis results of the HZO material film according to Experimental Examples 3-1 and 3-3 of the present invention.

[0045] Fig. 17 is a drawing for explaining the TEM analysis results of the HZO material film according to Experimental Examples 3-1 and 3-3 of the present invention.

[0046] FIG. 18 and FIG. 19 are drawings for explaining the area-selective deposition of the HZO material film according to Experimental Example 4 of the present invention.

[0047] Figure 20 is a drawing for explaining the XPS analysis results of the HZO material film according to Experimental Examples 6-1 and 6-3 of the present invention.

[0048] Figure 21 is a drawing for comparing the XPS analysis results of HZO material films according to Experimental Examples 3-1, 5-1, and 6-1 of the present invention.

[0049] Figure 22 is a drawing for comparing the XPS analysis results of HZO material films according to Experimental Examples 3-3, 5-3, and 6-3 of the present invention.

[0050] Figures 23 and 24 are drawings explaining the results of XRD analysis to confirm the crystallinity of the HZO material film according to experimental examples of the present invention.

[0051] FIG. 25 is a drawing for explaining the current-voltage curve of a capacitor according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0052] FIG. 26 is a drawing for explaining the dielectric constant-voltage curve of a capacitor according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0053] FIG. 27 is a drawing for explaining the polarity-voltage curve of a capacitor according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0054] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings. However, the technical concept of the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and to sufficiently convey the spirit of the present invention to those skilled in the art.

[0055] In this specification, when a component is referred to as being on another component, it means that it can be formed directly on the other component, or a third component may be interposed between them. In addition, in the drawings, the thicknesses of films and regions are exaggerated for the purpose of effectively explaining the technical contents.

[0056] Also, although terms such as first, second, and third have been used to describe various components in various embodiments of this specification, these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiments. Also, the term "and / or" has been used herein to mean including at least one of the components listed before and after.

[0057] In the specification, singular expressions include plural expressions unless the context clearly dictates otherwise. In addition, terms such as "comprise" or "have" are intended to specify the presence of a feature, number, step, component, or combination thereof described in the specification, and should not be construed as excluding the presence or addition of one or more other features, numbers, steps, components, or combinations thereof. In addition, the term "connection" is used in the present specification to mean both indirectly connecting multiple components and directly connecting them.

[0058] In addition, when describing the present invention below, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.

[0059]

[0060] FIG. 1 is a flowchart for explaining a region-selective atomic layer deposition method according to an embodiment of the present invention, FIG. 2 is a diagram for explaining step S100 of the region-selective atomic layer deposition method according to an embodiment of the present invention, FIG. 3 is a diagram for explaining step S200 of the region-selective atomic layer deposition method according to an embodiment of the present invention, FIGS. 4 and 5 are diagrams for explaining step S300 of the region-selective atomic layer deposition method according to an embodiment of the present invention, and FIG. 6 is a diagram for explaining a precursor volume used in step S300 of the region-selective atomic layer deposition method according to an embodiment of the present invention.

[0061] Referring to FIGS. 1 and 2, a first region (A1) including a metal layer (210) and a second region (excluding the first region (A1)) A2) is prepared (S100). That is, the substrate is divided into a first region (A1) and a second region (A2), and the second region (A2) is defined as a region excluding the first region (A1), and the metal layer (210) may be disposed on the first region (A1) of the substrate (100). For example, the substrate (100) may be a silicon oxide (SiO2) substrate.

[0062] According to one embodiment, the metal layer (210) may include a metal capable of inducing surface catalysis. For example, the metal layer (210) may include titanium nitride (TiN), ruthenium (Ru), platinum (Pt), tantalum nitride (TaN), ruthenium oxide (RuO2), tungsten (W), or tungsten nitride (WN). x , x>0), molybdenum (Mo), and molybdenum nitride (MoN x , x>0) can contain any one of them.

[0063] Referring to FIGS. 1 and 3, oxygen gas (O2gas) may be provided on the substrate (100) to activate the metal layer (210) of the first region (A1) (S200). The metal layer before activation is defined by reference numeral 210, and the metal layer in an activated state is defined by reference numeral 220.

[0064] More specifically, when oxygen gas is provided on the substrate (100), oxygen molecules (O2) of the oxygen gas can be dissociatively chemisorbed on the surface of the metal layer (210) by the surface catalytic action of the metal layer (210). Accordingly, oxygen atoms (O) are formed on the surface of the metal layer (210). *) is adsorbed, the metal layer (210) can be activated. Unlike the first region (A1), the second region (A2) is in a state where the substrate (100) is exposed without the metal layer (210), so that the oxygen molecules (O2) of the oxygen gas may not be dissociatively chemically adsorbed. As a result, oxygen atoms (O) are present in the second region (A2) of the substrate (100). * ) may not be absorbed.

[0065] Referring to FIG. 1 and FIG. 4 to FIG. 6, a first precursor (1) containing hafnium (Hf) is formed on the substrate (100). st Precursor), a second precursor (2) containing zirconium (Zr) nd Precursor), and reactant are provided to form HZO (Hf) on the activated metal layer (220) of the first region (A1) among the first region (A1) and the second region (A2). 1-x Zr x O2, x>0) material film (300) can be selectively deposited (S300). That is, the HZO material film (300) can be deposited on the activated metal layer (220) using atomic layer deposition (ALD).

[0066] According to one embodiment, the step (S300) of selectively depositing the HZO material film (300) on the activated metal layer (220) of the first region (A1) may include a step of providing the first precursor and the reactant on the substrate (100) to form a first material film (not shown) including HfO2 reacted with the first precursor and the reactant, and a step of providing the second precursor and the reactant on the first material film to form a second material film (not shown) including ZrO2 reacted with the second precursor and the reactant.

[0067] More specifically, the step of forming the first material film is to form the first precursor (1) on the substrate (100). st The method may include a step (S311) of providing a precursor, a first purge step (S312) for removing impurities and byproducts on the substrate (100) on which the first precursor is provided, a step (S313) of providing the reactant on the substrate (100), and a second purge step (S314) for removing impurities and byproducts on the substrate (100) on which the reactant is provided.

[0068] The step of forming the second material film comprises: forming a second precursor (2) on the first material film nd The method may include a step (S321) of providing a precursor, a first purge step (S322) for removing impurities and byproducts on the first material film to which the second precursor is provided, a step (S323) of providing the reactant on the first material film, and a second purge step (S324) for removing impurities and byproducts on the first material film to which the reactant is provided.

[0069] As illustrated in FIG. 5, steps S311, S312, S313, and S314 are steps of the first unit process (1 st Unit Process). In contrast, steps S321, S322, S323, and S324 may be defined as a second unit process (2 nd It can be defined as a Unit Process. In addition, the first unit process and the second unit process can be defined as a total process.

[0070] The first unit process and the second unit process may each be repeatedly performed multiple times. According to one embodiment, the repetition ratio of the second unit process to the repetition ratio of the first unit process may be 2:3. The composition of hafnium (Hf) and zirconium (Zr) in the HZO material film (300) may be controlled by the repetition ratio of the first unit process and the second unit process.

[0071] The first precursor and the second precursor may include a cyclopentadienyl ligand. For example, as illustrated in (a) of FIG. 6, the first precursor may include CpHf(NMe2)3 (cyclopentadienyl-tris(dimethylamino)-hafnium). Additionally, as illustrated in (b) of FIG. 6, the second precursor may include CpZr(NMe2)3 (cyclopentadienyl-tris(dimethylamino)-zirconium).

[0072] For precursors containing cyclopentadienyl ligands, they do not react with oxygen molecules (O2) below a certain temperature, but oxygen atoms (O) generated by dissociative adsorption of oxygen molecules * ) can react with. That is, by using a precursor including a cyclopentadienyl ligand, the reaction of the first precursor and the reactant and the reaction of the second precursor and the reactant can occur only on the activated metal layer (220). Accordingly, since the first material film (HfO2) and the second material film (ZrO2) are formed only on the activated metal layer (220), the HZO material film (300) can be selectively formed on the activated metal layer (220) of the first region (A1) among the first region (A1) and the second region (A2).

[0073] Oxygen (O2) may be used as the reactant. Accordingly, the HZO material film (300) may be crystallized into a tetragonal phase due to the heat treatment process described below. In contrast, when ozone (O3) is used as the reactant, a difference may occur in which the HZO material film (300) is crystallized into an orthorhombic phase due to the heat treatment process described below.

[0074] According to one embodiment, after the step (S300) of selectively depositing the HZO material film (300) on the activated metal layer (220) of the first region (A1), a step of ozone treating the HZO material film (300) may be further performed. Since the HZO material film (300) deposited through the steps S100 to S300 contains a number of impurities such as carbon (C), ozone treatment may be performed to remove them. That is, by ozone treatment of the HZO material film (300), impurities such as carbon (C) in the HZO material film (300) may be removed. When a number of impurities such as carbon (C) exist in the HZO material film (300), a problem of film quality deterioration (reliability deterioration) of the HZO material film (300) may occur. Therefore, by removing impurities such as carbon (C) in the HZO material film (300), the film quality of the HZO material film (300) can be improved (reliability improved).

[0075] In addition, according to one embodiment, after the step (S300) of selectively depositing the HZO material film (300) on the activated metal layer (220) of the first region (A1), a step of heat-treating the HZO material film (300) may be further performed. When the HZO material film (300) is heat-treated, the HZO material film (300) may be crystallized into a tetragonal phase. The HZO material film (300) crystallized into a tetragonal phase may exhibit anti-ferroelectric characteristics. In contrast, when the HZO material film (300) is crystallized into an orthorhombic phase (when O3 is used as a reactant), the anti-ferroelectric characteristics may not be exhibited.

[0076] As a result, the region-selective atomic layer deposition method according to an embodiment of the present invention comprises the steps of (S100) preparing a substrate (100) including a first region (A1) including a metal layer (210) and a second region (A2) excluding the first region (A1), the step of activating the metal layer (210) of the first region (A1) by providing oxygen gas on the substrate (100) (S200), and the step of providing a first precursor including hafnium (Hf), a second precursor including zirconium (Zr), and a reactant on the substrate (100) to form HZO (Hf) on the metal layer (220) of the first region (A1) among the first region (A1) and the second region (A2). 1-x Zr x A step of selectively depositing a material film (300) of O2, x>0) may be included. Accordingly, the HZO material film (300) can be selectively deposited on a specific region without using an inhibitor.

[0077] In addition, after the HZO material film (300) is selectively deposited on the metal layer (220) of the first region (A1), the HZO material film (300) can be ozone treated and heat treated. Accordingly, impurities (carbon, etc.) in the HZO material film (300) are removed and crystallized into a tetragonal phase, so that the HZO material film (300) can have a high dielectric constant value, exhibit anti-ferroelectric characteristics, and exhibit stable leakage current characteristics.

[0078]

[0079] Above, the region-selective atomic layer deposition method according to an embodiment of the present invention has been described. Hereinafter, application examples of the region-selective atomic layer deposition method according to an embodiment of the present invention will be described.

[0080] FIG. 7 is a drawing for explaining a gapfill process using an area-selective atomic layer deposition method according to an embodiment of the present invention.

[0081] Referring to FIG. 7, a gap-fill process is described for filling the space between the metal patterns (420) with a HZO material film (300) in a structure including a metal layer (410) and metal patterns (420) disposed on the metal layer (410).

[0082] The metal layer (410) and the metal pattern (420) may be composed of metals having different dissociation properties for oxygen molecules. For example, the metal layer (410) may be composed of a metal having relatively high dissociation properties, while the metal pattern (420) may be composed of a metal having relatively low dissociation properties. Thereafter, oxygen gas may be provided on the metal layer (410) and the metal pattern (420) to activate them, and then a HZO material film (300) may be formed by atomic layer deposition using a precursor containing a cyclopentadienyl ligand and a reactant containing oxygen (O2).

[0083] In this case, since the metal layer (410) has relatively high dissociation compared to the metal pattern (420), the HZO material film (300) can be formed on the metal layer (410) at a relatively high deposition rate, while the HZO material film (300) can be formed on the metal pattern (420) at a relatively low deposition rate. Accordingly, the space between the metal patterns (420) can be filled with the HZO material film (300), but the occurrence of voids and seams can be significantly reduced.

[0084] FIGS. 8 to 10 are drawings for explaining a process in which an area-selective atomic layer deposition method according to an embodiment of the present invention is applied to a capacitor having a filler-type lower electrode, and FIGS. 11 to 13 are drawings for explaining a process in which an area-selective atomic layer deposition method according to an embodiment of the present invention is applied to a capacitor having a siliter-type lower electrode.

[0085] As described above, titanium nitride (TiN) can be used as the metal layer of the area-selective atomic layer deposition method according to an embodiment of the present invention. Since titanium nitride (TiN) is a material used as an electrode in DRAM, the area-selective atomic layer deposition method described above can be easily applied to DRAM.

[0086] Referring to FIGS. 8 to 10, when a filler-type lower electrode (510) is placed on a transistor (500), oxygen gas is supplied to the lower electrode (510) to activate it, and then a HZO material film (300) can be formed by atomic layer deposition using a precursor containing a cyclopentadienyl ligand and a reactant containing oxygen (O2). Thereafter, by forming an upper electrode (520) to cover the HZO material film (300), a capacitor can be formed on the transistor (500).

[0087] Referring to FIGS. 11 to 13, when a cylinder-type lower electrode (510) is placed on a transistor (500), oxygen gas is supplied to the lower electrode (510) to activate it, and then a HZO material film (300) can be formed by atomic layer deposition using a precursor containing a cyclopentadienyl ligand and a reactant containing oxygen (O2). Thereafter, an upper electrode (520) is formed to cover the HZO material film (300), thereby forming a capacitor on the transistor (500).

[0088]

[0089] Above, application examples of the region-selective atomic layer deposition method according to an embodiment of the present invention have been described. Hereinafter, a region-selective atomic layer deposition apparatus according to an embodiment of the present invention will be described.

[0090] A region-selective atomic layer deposition device according to an embodiment of the present invention may include a chamber, an oxygen gas supply unit, a precursor supply unit, and a reactant supply unit. Each component is described below.

[0091] The chamber may have a space in which a substrate is disposed, the substrate including a first region including a metal layer and a second region excluding the second region. That is, the substrate is divided into a first region and a second region, wherein the second region is defined as a region excluding the first region, and the metal layer may be disposed on the first region of the substrate. According to one embodiment, the metal layer may include a metal capable of inducing a surface catalytic action. For example, the metal layer may include titanium nitride (TiN), ruthenium (Ru), platinum (Pt), tantalum nitride (TaN), ruthenium oxide (RuO2), tungsten (W), or tungsten nitride (WN). x , x>0), molybdenum (Mo), and molybdenum nitride (MoN x , x>0) can contain any one of them.

[0092] The above oxygen gas supply unit can provide oxygen gas into the chamber. When oxygen gas is supplied into the chamber, the metal layer of the first region can be activated. More specifically, when oxygen gas is provided on the substrate, oxygen molecules (O2) of the oxygen gas can be dissociatively chemisorbed on the surface of the metal layer by the surface catalytic action of the metal layer. Accordingly, oxygen atoms (O) are formed on the surface of the metal layer. * ) is adsorbed, the metal layer can be activated. Unlike the first region, the second region is a state in which the substrate is exposed without the metal layer, so that the oxygen molecules (O2) of the oxygen gas may not be dissociatively chemically adsorbed. As a result, the second region of the substrate may have oxygen atoms (O * ) may not be absorbed.

[0093] The precursor supply unit may provide a first precursor including hafnium (Hf) and a second precursor including zirconium (Zr) into the chamber. In one embodiment, the first precursor and the second precursor may include a cyclopentadienyl ligand. For example, the first precursor may include CpHf(NMe2)3 (cyclopentadienyl-tris(dimethylamino)-hafnium), and the second precursor may include CpZr(NMe2)3 (cyclopentadienyl-tris(dimethylamino)-zirconium).

[0094] The above-mentioned reactant supply unit can supply a reactant into the chamber. In one embodiment, the reactant may include oxygen (O2). When the reactant is supplied into the chamber, the reactant may react with the first precursor and the second precursor.

[0095] The first precursor, the second precursor, and the reactant provided into the chamber can react only on the activated metal layer. Accordingly, HZO (Hf) is formed on the metal layer of the first region among the first region and the second region. 1-x Zr x O2, x>0) material film can be selectively deposited.

[0096]

[0097] Above, a region-selective atomic layer deposition device according to an embodiment of the present invention has been described. Hereinafter, a region-selective atomic layer deposition method according to an embodiment of the present invention and specific experimental examples and characteristic evaluation results of a HZO material film formed thereby are described.

[0098] Deposition of HZO material film according to Experimental Example 1-1

[0099] A HZO material film was deposited on a SiO2 substrate by atomic layer deposition (ALD), using TEMAHf (tetrakis-(ethylmethylamido)-hafnium) as a Hf precursor and TEMAZr (tetrakis-(ethylmethylamido)-zirconium) as a Zr precursor. In addition, O2 was used as a reactant.

[0100]

[0101] Deposition of HZO material film according to Experimental Example 1-2

[0102] A HZO material film was deposited on a SiO2 substrate by atomic layer deposition (ALD), using TEMAHf (tetrakis-(ethylmethylamido)-hafnium) as a Hf precursor and TEMAZr (tetrakis-(ethylmethylamido)-zirconium) as a Zr precursor. In addition, O3 was used as a reactant.

[0103]

[0104] Deposition of HZO material film according to Experimental Example 1-3

[0105] A HZO material film was deposited on a SiO2 substrate by atomic layer deposition (ALD), using CpHf(NMe2)3(cyclopentadienyl-tris(dimethylamino)-hafnium) as a Hf precursor and CpZr(NMe2)3(cyclopentadienyl-tris(dimethylamino)-zirconium) as a Zr precursor. In addition, O2 was used as a reactant.

[0106]

[0107] Deposition of HZO material film according to Experimental Example 1-4

[0108] A HZO material film was deposited on a SiO2 substrate by atomic layer deposition (ALD), using CpHf(NMe2)3(cyclopentadienyl-tris(dimethylamino)-hafnium) as a Hf precursor and CpZr(NMe2)3(cyclopentadienyl-tris(dimethylamino)-zirconium) as a Zr precursor. In addition, O3 was used as a reactant.

[0109] Classification Hf precursor Zr precursor Reactant Experimental example 1-1 (Ex 1-1) TEMAHfTEMAZrO2 Experimental example 1-2 (Ex 1-2) TEMAHfTEMAZrO3 Experimental example 1-3 (Ex 1-3) CpHf(NMe2)3CpZr(NMe2)3O2 Experimental example 1-4 (Ex 1-4) CpHf(NMe2)3CpZr(NMe2)3O3

[0110] Figure 14 is a drawing for explaining the combination of precursors and reactants for forming a HZO material film using atomic layer deposition.

[0111] Referring to (a) of Fig. 14, the thickness (thickness, nm) of the HZO material film deposited according to the above experimental examples 1-1 to 1-4 is measured and shown, and referring to (b) of Fig. 14, the areal density (ng / cm) at the deposition process temperature conditions after depositing the HZO material film according to the above experimental examples 1-3 and 1-4 by changing the ALD process temperature is shown. 2 ) is measured and shown. In addition, Fig. 14 (a) shows the result of deposition at a temperature of 250°C.

[0112] As can be seen in (a) of Fig. 14, it was confirmed that when TEMAHf and TEMAZr were used as Hf precursors and Zr precursors (Ex 1-1, 1-2), the deposition of HZO material films occurred regardless of the reactant. On the other hand, when CpHf(NMe2)3 and CpZr(NMe2)3 were used as Hf precursors and Zr precursors, it was confirmed that deposition occurred through the O3 reactant (Ex 1-4), but not through the O2 reactant (Ex 1-3).

[0113] In addition, as can be confirmed in (b) of Fig. 14, when CpHf(NMe2)3 and CpZr(NMe2)3 were used as Hf precursor and Zr precursor, it was confirmed that no reaction with the O2 reactant occurred at all at an ALD process temperature below 320°C. In other words, it can be seen that when CpHf(NMe2)3 and CpZr(NMe2)3 precursors are used, the formation of a HZO material film on SiO2 can be prevented by using O2 as a reactant.

[0114]

[0115] Deposition of HZO material film according to Experimental Example 2-1

[0116] A HZO material film was deposited on a ruthenium (Ru) substrate by atomic layer deposition (ALD), using CpHf(NMe2)3 as a Hf precursor, CpZr(NMe2)3 as a Zr precursor, and O2 as a reactant, at a temperature of 250°C.

[0117]

[0118] Deposition of HZO material film according to Experimental Example 2-2

[0119] A HZO material film was deposited on a platinum (Pt) substrate by atomic layer deposition (ALD), using CpHf(NMe2)3 as a Hf precursor, CpZr(NMe2)3 as a Zr precursor, and O2 as a reactant, at a temperature of 250°C.

[0120]

[0121] Deposition of HZO material film according to Experimental Example 2-3

[0122] A HZO material film was deposited on a titanium nitride (TiN) substrate by atomic layer deposition (ALD), using CpHf(NMe2)3 as a Hf precursor, CpZr(NMe2)3 as a Zr precursor, and O2 as a reactant, at a temperature of 250°C.

[0123]

[0124] Deposition of HZO material film according to Experimental Example 2-4

[0125] A HZO material film was deposited on a silicon (Si) substrate by atomic layer deposition (ALD), using CpHf(NMe2)3 as a Hf precursor, CpZr(NMe2)3 as a Zr precursor, and O2 as a reactant, at a temperature of 250°C.

[0126]

[0127] Deposition of HZO material film according to Experimental Example 3-1

[0128] A HZO material film was deposited on a ruthenium (Ru) substrate by atomic layer deposition (ALD), using CpHf(NMe2)3 as a Hf precursor, CpZr(NMe2)3 as a Zr precursor, and O2 as a reactant, at a temperature of 280°C.

[0129]

[0130] Deposition of HZO material film according to Experimental Example 3-2

[0131] A HZO material film was deposited on a platinum (Pt) substrate by atomic layer deposition (ALD), using CpHf(NMe2)3 as a Hf precursor, CpZr(NMe2)3 as a Zr precursor, and O2 as a reactant, at a temperature of 280°C.

[0132]

[0133] Deposition of HZO material film according to Experimental Example 3-3

[0134] A HZO material film was deposited on a titanium nitride (TiN) substrate by atomic layer deposition (ALD), using CpHf(NMe2)3 as a Hf precursor, CpZr(NMe2)3 as a Zr precursor, and O2 as a reactant, at a temperature of 280°C.

[0135]

[0136] Deposition of HZO material film according to Experimental Example 3-4

[0137] A HZO material film was deposited on a silicon (Si) substrate by atomic layer deposition (ALD), using CpHf(NMe2)3 as a Hf precursor, CpZr(NMe2)3 as a Zr precursor, and O2 as a reactant, at a temperature of 280°C.

[0138] Separator substrate material Hf precursor Zr precursor Reactant material ALD process temperature Experimental example 2-1 (Ex 2-1) RuCpHf(NMe2)3CpZr(NMe2)3O2 250℃ Experimental example 2-2 (Ex 2-2) PtCpHf(NMe2)3CpZr(NMe2)3O2 250℃ Experimental example 2-3 (Ex 2-3) TiNCpHf(NMe2)3CpZr(NMe2)3O2 250℃ Experimental example 2-4 (Ex 2-4) SiCpHf(NMe2)3CpZr(NMe2)3O2 250℃ Experimental example 3-1 (Ex 3-1) RuCpHf(NMe2)3CpZr(NMe2)3O2 280℃ Experimental example 3-2 (Ex 3-2) PtCpHf(NMe2)3CpZr(NMe2)3O2280℃Experimental Example 3-3(Ex 3-3) TiNCpHf(NMe2)3CpZr(NMe2)3O2280℃Experimental Example 3-4(Ex 3-4) SiCpHf(NMe2)3CpZr(NMe2)3O2280℃

[0139] Figure 15 is a drawing for explaining the combination of a reactant material and a substrate material for forming a HZO material film using an atomic layer deposition method.

[0140] Referring to (a) of Fig. 15, the areal density (ng / cm) of the HZO material film deposited according to the experimental examples 2-1 to 2-4 2 ) is measured and shown, and referring to (b) of Fig. 15, the areal density (ng / cm) of the HZO material film deposited according to the experimental examples 3-1 to 3-4 is shown. 2 ) is measured and displayed.

[0141] As can be seen in (a) and (b) of Fig. 15, when an O2 reactive material was used, the formation of an HZO material film was easily achieved on ruthenium (Ru), platinum (Pt), and titanium nitride (TiN), but it was confirmed that the formation of an HZO material film was hardly achieved on silicon (Si).

[0142] As a result, as can be seen in FIGS. 14 and 15, when an HZO material film is deposited on a substrate (SiO2) including a first region including a metal layer and a second region excluding the first region by an ALD process, it can be seen that an HZO material film can be selectively formed on the metal layer of the first region excluding the second region by using a precursor including a cyclopentadienyl ligand and an O2 reactive material.

[0143] Fig. 16 is a drawing for explaining the XPS analysis results of the HZO material film according to Experimental Examples 3-1 and 3-3 of the present invention.

[0144] Referring to (a) and (b) of Fig. 16, the results of XPS (X-ray Photoelectron Spectroscopy) analysis are shown for the HZO material film (Ex 3-1) according to Experimental Example 3-1 and the HZO material film (Ex 3-3) according to Experimental Example 3-3, respectively. As can be confirmed from (a) and (b) of Fig. 16, it can be confirmed that carbon impurities are contained within the HZO material film manufactured by the ALD process.

[0145] Fig. 17 is a drawing for explaining the TEM analysis results of the HZO material film according to Experimental Examples 3-1 and 3-3 of the present invention.

[0146] Referring to (a) and (b) of FIG. 17, TEM (Transmission Electron Microscopy) images of the HZO material film (Ex 3-1) according to the experimental example 3-1 are shown, and referencing (c) and (d) of FIG. 17, TEM images of the HZO material film (Ex 3-3) according to the experimental example 3-3 are shown.

[0147] As can be seen in (a) and (b) of FIG. 17, an HZO material film is deposited on a ruthenium (Ru) substrate with a thickness of 7.1 nm after 200 cycles of ALD process, and as can be seen in (c) and (d) of FIG. 17, an HZO material film is deposited on a titanium nitride (TiN) substrate with a thickness of 6.9 nm after 300 cycles of ALD process.

[0148]

[0149] Area-selective deposition of HZO material film according to Experimental Example 4

[0150] After preparing a silicon (Si) substrate on which multiple platinum (Pt) patterns were formed, oxygen (O2) gas was provided to activate the surfaces of the platinum (Pt) patterns. Subsequently, a HZO material film was selectively deposited on the platinum (Pt) patterns using atomic layer deposition (ALD). CpHf(NMe2)3 was used as a Hf precursor, CpZr(NMe2)3 was used as a Zr precursor, and O2 was used as a reactant.

[0151]

[0152] FIG. 18 and FIG. 19 are drawings for explaining the area-selective deposition of the HZO material film according to Experimental Example 4 of the present invention.

[0153] Fig. 18 (a) shows a schematic diagram for explaining the process of area-selective deposition of the HZO material film according to the experimental example 4, and Fig. 18 (b) to (e) show the results of SEM (Scanning Electron Microscopy) - EDS (Energy Dispersive X-Ray Spectrometer) elemental mapping. In addition, Fig. 19 (a) to (e) show the results of TEM (Transmission Electron Microscopy) - EELS (Electron Energy Loss Spectrometer) elemental mapping.

[0154] As can be seen in FIGS. 18 and 19, the HZO material film is not deposited on the substrate (Si) region without the platinum (Pt) pattern, and the HZO material film is selectively deposited only on the platinum (Pt) pattern.

[0155]

[0156] Deposition of HZO material film according to Experimental Example 5-1

[0157] An HZO material film was deposited using the method according to Experimental Example 3-1 described above, but O3 was used as a reactant.

[0158]

[0159] Deposition of HZO material film according to Experimental Example 6-1

[0160] After depositing the HZO material film by the method according to Experimental Example 3-1 described above, the deposited HZO material film was treated with ozone (O3).

[0161] Substrate material reaction material subsequent ozone treatment experiment Example 3-1 (Ex 3-1) RuO2X Experiment Example 5-1 (Ex 5-1) RuO3X Experiment Example 6-1 (Ex 6-1) RuO2O

[0162] Deposition of HZO material film according to Experimental Example 5-3

[0163] An HZO material film was deposited using the method according to Experimental Example 3-3 described above, but O3 was used as a reactant.

[0164]

[0165] Deposition of HZO material film according to Experimental Example 6-3

[0166] After depositing the HZO material film by the method according to Experimental Example 3-3 described above, the deposited HZO material film was treated with ozone (O3).

[0167] Substrate material reaction material subsequent ozone treatment experiment Example 3-3 (Ex 3-3) TiNO2X Experiment Example 5-3 (Ex 5-3) TiNO3X Experiment Example 6-3 (Ex 6-3) TiNO2O

[0168] Figure 20 is a drawing for explaining the XPS analysis results of the HZO material film according to Experimental Examples 6-1 and 6-3 of the present invention.

[0169] Referring to (a) and (b) of FIG. 20, the results of XPS (X-ray Photoelectron Spectroscopy) analysis are shown for the HZO material film (Ex 6-1) according to Experimental Example 6-1 and the HZO material film (Ex 6-3) according to Experimental Example 6-3, respectively. As can be seen in (a) and (b) of FIG. 20, it can be confirmed that carbon impurities are removed as ozone treatment is performed on the deposited HZO material film after the HZO material film is deposited.

[0170] Figure 21 is a drawing for comparing the XPS analysis results of HZO material films according to Experimental Examples 3-1, 5-1, and 6-1 of the present invention.

[0171] Referring to (a) to (d) of FIG. 21, the XPS analysis results for each of the HZO material films according to Experimental Example 3-1 (Ex 3-1), Experimental Example 5-1 (Ex 5-1), and Experimental Example 6-1 (Ex 6-1) are shown. As can be seen in (a) of FIG. 21, it can be confirmed that carbon impurities are removed as ozone treatment is performed on the deposited HZO material film after the HZO material film is deposited.

[0172] Figure 22 is a drawing for comparing the XPS analysis results of HZO material films according to Experimental Examples 3-3, 5-3, and 6-3 of the present invention.

[0173] Referring to (a) to (d) of FIG. 22, the XPS analysis results for each of the HZO material films according to Experimental Example 3-3 (Ex 3-3), Experimental Example 5-3 (Ex 5-3), and Experimental Example 6-3 (Ex 6-3) are shown. As can be seen in (a) of FIG. 22, it can be confirmed that carbon impurities are removed as ozone treatment is performed on the deposited HZO material film after the HZO material film is deposited.

[0174]

[0175] Deposition of HZO material film according to Experimental Example 7-1

[0176] After depositing the HZO material film by the method according to Experimental Example 3-1 described above, the deposited HZO material film was heat-treated at a temperature of 600°C for 10 seconds.

[0177]

[0178] Deposition of HZO material film according to Experimental Example 8-1

[0179] After depositing the HZO material film by the method according to Experimental Example 5-1 described above, the deposited HZO material film was heat-treated at a temperature of 600°C for 10 seconds.

[0180]

[0181] Deposition of HZO material film according to Experimental Example 9-1

[0182] After depositing the HZO material film by the method according to Experimental Example 6-1 described above, the deposited HZO material film was heat-treated at a temperature of 600°C for 10 seconds.

[0183] Substrate materialReaction materialSubsequent ozone treatmentSubsequent heat treatmentExperimental example 3-1 (Ex 3-1)RuO2XXExperimental example 5-1 (Ex 5-1)RuO3XXExperimental example 6-1 (Ex 6-1)RuO2OXExperimental example 7-1 (Ex 7-1)RuO2XOExperimental example 8-1 (Ex 8-1)RuO3XOExperimental example 9-1 (Ex 9-1)RuO2OO

[0184] Deposition of HZO material film according to Experimental Example 7-3

[0185] After depositing the HZO material film by the method according to Experimental Example 3-3 described above, the deposited HZO material film was heat-treated at a temperature of 600°C for 10 seconds.

[0186]

[0187] Deposition of HZO material film according to Experimental Example 8-3

[0188] After depositing the HZO material film by the method according to Experimental Example 5-3 described above, the deposited HZO material film was heat-treated at a temperature of 600°C for 10 seconds.

[0189]

[0190] Deposition of HZO material film according to Experimental Example 9-3

[0191] After depositing the HZO material film by the method according to Experimental Example 6-3 described above, the deposited HZO material film was heat-treated at a temperature of 600°C for 10 seconds.

[0192] Substrate materialReaction materialSubsequent ozone treatmentSubsequent heat treatmentExperimental example 3-3 (Ex 3-3)TiNO2XXExperimental example 5-3 (Ex 5-3)TiNO3XXExperimental example 6-3 (Ex 6-3)TiNO2OXExperimental example 7-3 (Ex 7-3)TiNO2XOExperimental example 8-3 (Ex 8-3)TiNO3XOExperimental example 9-3 (Ex 9-3)TiNO2OO

[0193] Figures 23 and 24 are drawings explaining the results of XRD analysis to confirm the crystallinity of the HZO material film according to experimental examples of the present invention.

[0194] Referring to FIG. 23, the XRD (X-ray diffraction) analysis results for each of the HZO material films according to Experimental Example 3-1 (Ex 3-1), Experimental Example 5-1 (Ex 5-1), Experimental Example 6-1 (Ex 6-1), Experimental Example 7-1 (Ex 7-1), Experimental Example 8-1 (Ex 8-1), and Experimental Example 9-1 (Ex 9-1) are shown.

[0195] Referring to FIG. 24, the XRD (X-ray diffraction) analysis results for each of the HZO material films according to Experimental Example 3-3 (Ex 3-3), Experimental Example 5-1 (Ex 5-3), Experimental Example 6-1 (Ex 6-3), Experimental Example 7-1 (Ex 7-3), Experimental Example 8-1 (Ex 8-3), and Experimental Example 9-1 (Ex 9-3) are shown.

[0196] As can be seen in FIGS. 23 and 24, it was confirmed that the HZO material films (Ex 3-1, 3-3, 5-1, 5-3, 6-1) that were not subjected to subsequent ozone treatment or subsequent heat treatment were in an amorphous state. On the other hand, it was confirmed that the HZO material films that were subjected to subsequent ozone treatment (Ex 6-1, 6-3, 9-1, 9-3) and the HZO material films that were subjected to subsequent heat treatment (Ex 7-1, 7-3, 8-1, 8-3, 9-1, 9-3) were crystallized.

[0197] In particular, when the HZO material film deposited using an O2 reactive material was subjected to subsequent heat treatment (Ex 7-1, 7-3, 9-1, 9-3), it was confirmed that the HZO material film was crystallized into a tetragonal phase. In contrast, when the HZO material film deposited using an O3 reactive material was subjected to subsequent heat treatment (Ex 8-1, 8-3), it was confirmed that the HZO material film was crystallized into an orthorhombic phase.

[0198]

[0199] Manufacturing of capacitors according to Experimental Example 1

[0200] A capacitor having a Ru / HZO / TiN structure was manufactured by depositing an HZO material film on a ruthenium (Ru) material film using atomic layer deposition (ALD) and depositing a titanium nitride (TiN) material film on the deposited HZO material film.

[0201] More specifically, CpHf(NMe2)3 was used as a Hf precursor for HZO material film deposition, CpZr(NMe2)3 was used as a Zr precursor, and O2 was used as a reactant, and the HZO material film was deposited under a temperature condition of 280°C. In addition, after the HZO material film deposition, the deposited HZO material film was treated with ozone (O3), and after a capacitor with a Ru / HZO / TiN structure was manufactured, the manufactured capacitor was heat-treated at a temperature of 600°C for 10 seconds.

[0202]

[0203] Manufacturing of capacitors according to Experimental Example 2

[0204] A capacitor having a TiN / HZO / TiN structure was manufactured by the method described in Experimental Example 1 above, but an HZO material film was deposited on a titanium nitride (TiN) material film by atomic layer deposition (ALD), and a titanium nitride (TiN) material film was deposited on the deposited HZO material film.

[0205] Discriminant capacitor structure experiment example 1 (Ex C1)Ru / HZO / TiN Experiment example 2 (Ex C2)TiN / HZO / TiN

[0206] FIG. 25 is a drawing for explaining the current-voltage curve of a capacitor according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0207] Referring to (a) and (b) of Fig. 25, current-voltage curves for each capacitor according to Experimental Example 1 (Ex C1) and Experimental Example 2 (Ex C2) are shown. As can be seen from (a) and (b) of Fig. 25, it was confirmed that both capacitors according to Experimental Example 1 and Experimental Example 2 had low leakage current characteristics of 300 nA level at +3 V.

[0208] FIG. 26 is a drawing for explaining the dielectric constant-voltage curve of a capacitor according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0209] Referring to (a) and (b) of Fig. 26, dielectric constant-voltage curves are shown for each capacitor according to Experimental Example 1 (Ex C1) and Experimental Example 2 (Ex C2). As can be seen from (a) and (b) of Fig. 26, it was confirmed that both capacitors according to Experimental Example 1 and Experimental Example 2 exhibited high dielectric constant values ​​exceeding 30 at 0 V.

[0210] FIG. 27 is a drawing for explaining the polarity-voltage curve of a capacitor according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0211] Referring to (a) and (b) of Fig. 27, polarization-voltage curves are shown for each capacitor according to Experimental Example 1 (Ex C1) and Experimental Example 2 (Ex C2). As can be seen from (a) and (b) of Fig. 27, it was confirmed that both capacitors according to Experimental Example 1 and Experimental Example 2 exhibited anti-ferroelectric properties. That is, it can be seen that anti-ferroelectric properties can be expressed by crystallizing the HZO material film into a tetragonal phase through subsequent heat treatment of the HZO material film.

[0212]

[0213] While the present invention has been described in detail using preferred embodiments, the scope of the present invention is not limited to the specific embodiments described above, and should be interpreted in accordance with the appended claims. Furthermore, those skilled in the art will appreciate that numerous modifications and variations are possible without departing from the scope of the present invention.

[0214] The present invention can be used in the material deposition industry.

Claims

1. A step of preparing a substrate including a first region including a metal layer and a second region excluding the first region; A step of activating the metal layer of the first region by providing oxygen gas on the substrate; and A first precursor containing hafnium (Hf), a second precursor containing zirconium (Zr), and a reactant are provided on the substrate, thereby forming HZO (Hf) on the metal layer of the first region among the first region and the second region. 1-x Zr x O 2 , x>0) a region-selective atomic layer deposition method comprising a step of selectively depositing a material film.

2. In paragraph 1, In the step of activating the metal layer of the first region, By the surface catalytic action of the metal layer, the oxygen molecules of the oxygen gas are dissociatively chemisorbed on the surface of the metal layer. A region-selective atomic layer deposition method comprising activating a metal layer by adsorbing oxygen atoms onto the surface of the metal layer.

3. In paragraph 1, The first precursor and the second precursor are a region-selective atomic layer deposition method comprising a cyclopentadienyl ligand.

4. In paragraph 3, A region-selective atomic layer deposition method wherein the first precursor comprises cyclopentadienyl-tris(dimethylamino)-hafnium, and the second precursor comprises cyclopentadienyl-tris(dimethylamino)-zirconium.

5. In paragraph 1, The above reactant is oxygen (O 2 ) region-selective atomic layer deposition method.

6. In paragraph 1, After the step of selectively depositing a HZO material film on the metal layer of the first region, The above HZO material film is ozone (O 3 ) further comprising a step of removing carbon (C) within the HZO material film.

7. In paragraph 1, After the step of selectively depositing a HZO material film on the metal layer of the first region, A region-selective atomic layer deposition method further comprising a step of heat-treating the HZO material film to crystallize the HZO material film into a tetragonal phase.

8. In paragraph 7, A region-selective atomic layer deposition method in which the HZO material film exhibits anti-ferroelectric properties as the HZO material film crystallizes into a tetragonal phase.

9. In paragraph 1, The step of selectively depositing a HZO material film on the metal layer of the first region is, The first precursor and the reactant are provided on the substrate, and the first precursor and the reactant are reacted to form HfO. 2 a step of forming a first material film including; and The second precursor and the reactant are provided on the first material film, so that the second precursor and the reactant are reacted to form ZrO. 2 A region-selective atomic layer deposition method comprising the step of forming a second material film including:

10. In paragraph 9, Since the reaction between the first precursor and the reactant and the reaction between the second precursor and the reactant occur on the activated metal layer, A region-selective atomic layer deposition method, wherein the first material film and the second material film are formed on the activated metal layer.

11. A chamber in which a substrate is placed, the chamber including a first region including a metal layer and a second region excluding the second region; An oxygen gas supply unit that supplies oxygen gas into the chamber to activate the metal layer of the first region; A precursor supply unit that provides a first precursor containing hafnium (Hf) and a second precursor containing zirconium (Zr) into the chamber; and Including a reaction material supply unit that provides a reaction material to react with the first precursor and the second precursor within the chamber, HZO (Hf) on the metal layer of the first region among the first region and the second region 1-x Zr x O 2 , x>0) A region-selective atomic layer deposition device including selectively depositing a material film.

12. In paragraph 11, A region-selective atomic layer deposition device, wherein the first precursor, the second precursor, and the reactant provided into the chamber react only on the activated metal layer.

13. A substrate including a first region including a metal layer and a second region excluding the first region, and HZO (Hf) formed on the metal layer of the first region 1-x Zr x O 2 , x>0) including a material film, An HZO material film structure including the above HZO material film crystallized in a tetragonal phase and exhibiting anti-ferroelectric properties.

14. In paragraph 13, The above metal layer is titanium nitride (TiN), ruthenium (Ru), platinum (Pt), tantalum nitride (TaN), ruthenium oxide (RuO 2 ), tungsten (W), tungsten nitride (WN) x , x>0), molybdenum (Mo), and molybdenum nitride (MoN x , HZO material film structure including any one of x>0.

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