Capacitor, electronic device including same, and method for manufacturing same

Abstract

To provide a capacitor, an electronic device including the same, and a method of manufacturing the capacitor.SOLUTION: A capacitor is provided, comprising: a first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer arranged between the first and second thin-film electrode layers; and an intermediate layer arranged at one or more of a portion between the first thin-film electrode layer and the dielectric layer and a portion between the second thin-film electrode layer and the dielectric layer. The intermediate layer has crystal structure in the same form as one or more layers among the electrode layers and the dielectric layer in contact with the intermediate layer and has a composition different from those of the above one or more layers. The intermediate layer includes a first anionized layer or a second anionized layer or a first neutral layer. The first anionized layer includes a monovalent or bivalent cation or a trivalent cation with an atom weight of 20 or more. The second anionized layer includes a monovalent cation. The first neutral layer includes a plurality of trivalent cations. An electronic device including the capacitor, and a method of manufacturing the capacitor are also provided.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] The present invention relates to a capacitor, an electronic device including the same, and a method for manufacturing the same. [Background technology]

[0002] 2. Description of the Related Art Semiconductor devices such as memories and transistors are used in a variety of home and industrial appliances. As the performance of home and industrial appliances improves, the integration and miniaturization of semiconductor devices is progressing.

[0003] As semiconductor devices become more highly integrated and miniaturized, their size is reduced. For example, as the size of a capacitor is reduced, the capacitance of the capacitor is reduced and leakage current increases. To solve these problems, various methods have been proposed.

[0004] For example, the capacitance of a capacitor can be maintained by changing the structure of the capacitor by increasing the electrode area of ​​the capacitor or reducing the dielectric thickness, or by improving the capacitor manufacturing process.

[0005] However, there is a limit to how much the capacitance of a capacitor can be maintained by structural improvements such as increasing the electrode area of ​​the capacitor or reducing the dielectric thickness, or by improvements in the manufacturing process.

[0006] Ternary oxide dielectric materials can be used to achieve high capacitance. Representative ternary oxide dielectrics are ternary oxides containing divalent cations and tetravalent cations, with a perovskite crystal structure in which the divalent cations, tetravalent cations, and oxygen have a composition ratio of 1:1:3. Examples of ternary oxide dielectrics include SrTiO3, CaTiO3, BaTiO3, SrHfO3, SrZrO3, and PbTiO3. Ternary oxide dielectrics are not limited to these materials; ternary oxides containing other cations can also be used as dielectrics. However, the band gap of these ternary oxide dielectrics is small, ranging from 3 eV to 4 eV, resulting in high leakage current between the electrodes and the dielectric.

[0007] Therefore, it is important to suppress leakage current between the electrode and the dielectric.

[0008] As a method for improving the leakage current characteristics between the electrode and the dielectric, a method for adjusting the Schottky barrier can be considered.

[0009] The Schottky barrier is the difference between the work function (Φ) of the electrode and the electron affinity (χ) of the dielectric film. When the electrode and the dielectric are in contact, their Fermi levels become the same, and an energy barrier called the Schottky barrier is formed at the interface between the electrode and the dielectric, suppressing charge transfer and improving leakage current. When the dielectric is an n-type semiconductor, the greater the work function of the electrode is than the electron affinity of the dielectric, the higher the Schottky barrier height (SBH).

[0010] To realize a high Schottky barrier height (SBH) between the dielectric and the electrode, the following conditions must be satisfied: the crystal structure and lattice constant of the dielectric and the electrode are similar, the stability of the interface between the dielectric and the electrode is high, and the work function of the electrode is greater than the electron affinity of the dielectric. However, it is not easy to realize a capacitor with a high Schottky barrier height between the dielectric and the electrode.

[0011] Therefore, a new capacitor is needed that has an increased Schottky barrier height between the dielectric and the electrodes compared to conventional capacitors, thereby suppressing leakage current. Summary of the Invention [Problem to be solved by the invention]

[0012] The problem to be solved by the present invention is to provide a capacitor in which leakage current is suppressed by including an intermediate layer having a new structure.

[0013] Another object of the present invention is to provide an electronic device including the dielectric.

[0014] Another object of the present invention is to provide a method for manufacturing the capacitor. [Means for solving the problem]

[0015] According to one aspect, a first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer disposed between the first thin-film electrode layer and the second thin-film electrode layer; and an interlayer disposed between the first thin-film electrode layer and the dielectric layer, and / or between the second thin-film electrode layer and the dielectric layer; the intermediate layer has the same type of crystal structure as at least one of the electrode layer and the dielectric layer in contact with the intermediate layer, but has a different composition from them; the intermediate layer comprises a first anionized layer, a second anionized layer, or a first neutral layer; the first anionization layer contains monovalent cations, divalent cations, or trivalent cations with an atomic weight of 20 or greater; the second anionization layer contains monovalent cations; A capacitor is provided wherein the first neutral layer includes a plurality of trivalent cations.

[0016] The first anionization layer is [B1O2] a- is expressed as B1 is a monovalent cation, a divalent cation, or a trivalent cation having an atomic weight of 20 or more; The a may be 1, 2 or 3.

[0017] B1 can be Li, Na, K, Rb, Cs, Mg, Be, Ba, Ca, Ga or In.

[0018] The first anionization layer is [GaO2] - , [InO2] - , [BeO2] 2- , [MgO2] 2- , [BaO2] 2- , [CaO2] 2- , [LiO2] 3- , [NaO2] 3- , [KO2] 3- or [RbO2] 3- It may be expressed as:

[0019] the intermediate layer comprises the first anionization layer; further comprising a second neutral layer; The second neutral layer may be represented by [A1O], where A1 is a divalent cation.

[0020] Said A1 can be Sr, Ca, Ba, Mg or Be.

[0021] The second neutral layer may be represented by [SrO], [CaO], [BaO], [MgO] or [BeO].

[0022] the intermediate layer comprises a first anionization layer and a second neutral layer; the first anionization layer and the second neutral layer are stacked on top of each other; The first anionization layer and the second neutral layer may contain different metals.

[0023] The intermediate layer may contain a metal oxide having a perovskite crystal structure represented by the following Chemical Formula 1: [Chemical formula 1] [A1B1O x ] In the above Chemical Formula 1, A1 is a divalent cation, B1 is a monovalent cation, a divalent cation, or a trivalent cation with an atomic weight of 20 or greater; 2.5 <x≦3.0である。

[0024] The intermediate layer is [SrGaO x ], [CaGaO x ], [BaGaO x ], [PbGaO x ], [SrInO x ], [CaInO x ], [BaInO x ], [PbInO x ], [SrBeO x ], [CaBeO x ], [BaBeO x ], [PbBeO x ], [SrMgO x ], [CaMgO x ], [BaMgO x ], [PbMgO x ], [SrBaO x ], [CaBaO x ], [PBBaO x ], [SrCaO x ], [BaCaO x ], [PbCaO x ], [SrLiO x ], [CaLiO x ], [BaLiO x ], [PbLiO x ], [SrNaO x ], [CaNaO x ], [BaNaO x ], [PbNaO x ] [SrKO x ], [CaKO x ], [BaKO x ], [PbKO x ], [SrRbO x ], [CaRbO x ], [BaRbO x ] or [PbRbO x

[0023] 2.5 <x≦3.0であってもよい。

[0025] The second anionization layer is [A2O] - wherein A2 can be a monovalent cation.

[0026] The A2 may be Li, Na, K, Rb or Cs.

[0027] The second anionization layer is [LiO] - , [NaO] - , [KO] - or [RbO] - It may be expressed as:

[0028] the intermediate layer comprises the second anionization layer; further comprising a third neutral layer; The third neutral layer may be represented by [B2O2], where B2 is a tetravalent cation.

[0029] The B2 may be Ti, Hf or Zr.

[0030] The third neutral layer is It may be represented by [TiO2], [ZrO2] or [HfO2].

[0031] The intermediate layer may include a metal oxide having a perovskite crystal structure represented by the following Chemical Formula 2: [Chemical formula 2] [A2B2O x ] In the above Chemical Formula 1, A2 is a monovalent cation, B2 is a tetravalent cation, 2.5≦x≦3.0.

[0032] The intermediate layer is [LiTiO x ], [NaTiO x ], [KTiO x ], [RbTiO x ], [LiZrO x ], [NaZrO x ], [KZrO x ], [RbZrO x ], [LiHfO x ], [NaHfO x ], [KHfO x ] or [RbHfO x

[0023] 2.5 <x≦3.0でありうる。

[0033] The first neutral layer may include a metal oxide having a perovskite crystal structure represented by the following Chemical Formula 3: [Chemical formula 3] [A3B3O3] In the above Chemical Formula 3, A3 is a trivalent cation, B3 is a trivalent cation.

[0034] The intermediate layer is [ScAlO3], [YAlO3], [LaAlO3], [CeAlO3], [PrAlO3], [NdAlO3], [SmAlO3], [DyAlO3], [ScGaO3], [YGaO3], [LaGaO3], [CeGaO3], [PrGaO3], [NdGaO3], [SmGaO3], [DyGaO3], It may contain a metal oxide selected from [ScInO3], [YInO3], [LaInO3], [CeInO3], [PrInO3], [NdInO3], [SmInO3] or [DyInO3].

[0035] The first neutral layer is [A3O] + A first cationized layer represented by [B3O2] - and a third anionization layer represented by The A3 may be a trivalent cation, the B3 may be a trivalent cation, and A3 and B3 may be different metals.

[0036] A3 is Sc, Y, La, Ce, Pr, Nd, Sm or Dy; The B3 can be Al, Ga or In.

[0037] The intermediate layer is [ScO] + , [YO] + , [LaO] + , [CeO] + , [PrO] + , [NdO] + , [SmO] + or [DyO] + A first cationized layer represented by [AlO2] - , [GaO2] - or [InO2] - and a third anionization layer represented by:

[0038] the intermediate layer comprises 1 to 3 unit cells, and the thickness of the intermediate layer is 1 to 15 Å; a Schottky barrier height (SBH) between the first thin-film electrode layer or the second thin-film electrode layer and the dielectric layer is 1.5 eV or more; The intermediate layer may be formed by epitaxial growth.

[0039] The dielectric layer may include a dielectric having a perovskite crystal structure represented by the following Chemical Formula 4: [Chemical formula 4] A4B4O3 In the above Chemical Formula 4, A4 is a monovalent, divalent, or trivalent cation; B4 is a trivalent, tetravalent or pentavalent cation.

[0040] The dielectric layer is The dielectric may include a dielectric selected from SrTiO3, CaTiO3, BaTiO3, SrHfO3, CaHfO3, BaHfO3, SrZrO3, CaZrO3, BaZrO3, PbTiO3, NaNbO3, NaTaO3, RbTaO3, RbNbO3, RbTaO3 or EuTiO3.

[0041] The thickness of the dielectric layer is 10 nm to 100 nm, The thickness of the first thin-film electrode layer and the second thin-film electrode layer is 10 nm to 1,000 nm, respectively; At least one of the first thin-film electrode layer and the second thin-film electrode layer may have a perovskite crystal structure.

[0042] According to another aspect, An electronic device is provided that includes a capacitor in accordance with the foregoing.

[0043] The electronic device may be a semiconductor device.

[0044] According to yet another aspect, providing a first thin-film electrode layer or a second thin-film electrode layer; disposing an intermediate layer on one surface of the first thin film electrode layer or the second thin film electrode layer by epitaxial growth; disposing a dielectric layer on the intermediate layer; and depositing another thin film electrode layer on the dielectric layer to provide a capacitor; the capacitor comprises: a first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer disposed between the first thin-film electrode layer and the second thin-film electrode layer; and an intermediate layer disposed between the first thin-film electrode layer and the dielectric layer, or between the second thin-film electrode layer and the dielectric layer; the intermediate layer has the same crystalline structure as one or more of the electrode layer and the dielectric layer in contact with the intermediate layer, but has a different composition from the electrode layer and the dielectric layer; the intermediate layer comprises a first anionizable layer, a second anionizable layer, or a first neutral layer; the first anionization layer contains monovalent cations, divalent cations, or trivalent cations with an atomic weight of 20 or greater; the second anionization layer contains monovalent cations; the first neutral layer comprises a plurality of trivalent cations; A method for manufacturing a capacitor is provided, wherein the dielectric layer comprises a ternary oxide with a perovskite crystal structure. [Effects of the Invention]

[0045] According to one aspect, the leakage current of the capacitor is reduced by including an intermediate layer having a novel structure. [Brief explanation of the drawings]

[0046] [Figure 1A] 1 is a schematic diagram of a capacitor including an intermediate layer according to an embodiment. [Figure 1B] 1 is an enlarged schematic view illustrating a structure of an intermediate layer portion of a capacitor including an intermediate layer according to an embodiment; [Figure 2A] 1 is a schematic diagram of a capacitor including an intermediate layer according to an embodiment. [Figure 2B] 1 is an enlarged schematic view illustrating a structure of an intermediate layer portion of a capacitor including an intermediate layer according to an embodiment; [Figure 3A]1 is a schematic diagram of a capacitor including an intermediate layer according to an embodiment. [Figure 3B] 1 is an enlarged schematic view illustrating a structure of an intermediate layer portion of a capacitor including an intermediate layer according to an embodiment; [Figure 4A] 1 is an enlarged schematic view illustrating a structure of an intermediate layer portion of a capacitor including an intermediate layer according to an embodiment; [Figure 4B] 1 is an enlarged schematic view illustrating a structure of an intermediate layer portion of a capacitor including an intermediate layer according to an embodiment; [Figure 5A] FIG. 1 is a schematic diagram of a capacitor according to an embodiment. [Figure 5B] FIG. 1 is a schematic diagram of a capacitor according to an embodiment. [Figure 5C] FIG. 1 is a schematic diagram of a capacitor according to an embodiment. [Figure 5D] FIG. 1 is a schematic diagram of a capacitor according to an embodiment. [Figure 6] 1 is a cross-sectional view showing a structure of a metal-insulator-metal (MIM) capacitor according to an embodiment. [Figure 7] 1 is a diagram illustrating a structure of a trench capacitor type dynamic random access memory (DRAM) according to an embodiment. [Figure 8] 1 is a cross-sectional view illustrating a memory device having a layered structure including a dielectric layer according to an embodiment; [Figure 9] 1 is a layout diagram illustrating a semiconductor device according to an embodiment; [Figure 10] 1 is a conceptual diagram illustrating a device architecture that can be applied to an electronic device according to an embodiment; [Figure 11] 1 is a conceptual diagram illustrating a device architecture that can be applied to an electronic device according to an embodiment; DETAILED DESCRIPTION OF THE INVENTION

[0047] The present inventive concept described below can be modified in various ways and can have various embodiments, but specific embodiments are illustrated in the drawings and described in detail. However, it should be understood that these do not limit the present inventive concept to specific embodiments, but include all modifications, equivalents, or alternatives that fall within the technical scope of the present inventive concept.

[0048] The terms used below are merely used to describe specific embodiments and are not intended to limit the present invention. A singular expression includes a plural expression unless the context clearly dictates otherwise. Hereinafter, terms such as "comprise" or "have" indicate the presence of a feature, number, step, operation, component, part, ingredient, material, or combination thereof described in the specification, and should be understood not to preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, ingredients, materials, or combinations thereof. The " / " used below can be interpreted as either "and" or "or," depending on the context.

[0049] In the drawings, thicknesses may be exaggerated or reduced to clearly depict various layers and regions. Similar parts are designated by the same reference numerals throughout the specification. Throughout the specification, when a part, such as a layer, film, region, or plate, is described as being "on" or "above" another part, this refers not only to being directly on top of the other part, but also to being between other parts. Throughout the specification, terms such as "first" and "second" may be used to describe various components, but the components are not limited by these terms. These terms are used only to distinguish one component from another. Throughout the specification and drawings, components having substantially the same function and configuration will be referred to by the same reference numerals, and redundant description will be omitted.

[0050] Hereinafter, a capacitor according to example embodiments, an electronic device including the same, and a method for manufacturing the capacitor will be described in further detail.

[0051] A capacitor according to one embodiment includes a first thin-film electrode layer, a second thin-film electrode layer, a dielectric layer disposed between the first and second thin-film electrode layers, and an interlayer disposed between the first thin-film electrode layer and the dielectric layer and / or between the second thin-film electrode layer and the dielectric layer, the interlayer having the same crystal structure as at least one of the electrode layer and the dielectric layer in contact with the interlayer but a different composition from the electrode layer and / or the dielectric layer, the interlayer including a first anionized layer, a second anionized layer, or a first neutral layer, the first anionized layer including monovalent cations, divalent cations, or trivalent cations with an atomic weight of 20 or more, the second anionized layer including monovalent cations, and the first neutral layer including a plurality of trivalent cations. For example, the first anionized layer including monovalent cations, divalent cations, or trivalent cations with an atomic weight of 40 or more.

[0052] The intermediate layer includes a first anionization layer, a second anionization layer, or a first neutral layer, which induces screening charges in the adjacent thin-film electrode layer. Such screening electrons induce an additional electrostatic potential difference between the thin-film electrode layer and the dielectric layer. Therefore, the Schottky barrier height (SBH) between the thin-film electrode layer and the dielectric layer is further increased, resulting in reduced leakage current in a capacitor including the intermediate layer. For example, the first anionization layer and the second anionization layer have negative charges, which induce positive screening charges in the adjacent thin-film electrode layer. For example, the first neutral layer is neutral overall, but the first neutral layer includes a third positive charge layer and a first negative charge layer, which induce screening charges in the adjacent thin-film electrode layer. As a result, the leakage current of a capacitor including such an intermediate layer is reduced.

[0053] 1A and 1B, the capacitor includes a first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer disposed between the first thin-film electrode layer and the second thin-film electrode layer; and an intermediate layer disposed between the first thin-film electrode layer and the dielectric layer and / or between the second thin-film electrode layer and the dielectric layer, the intermediate layer including a first anionization layer. The first thin-film electrode layer, the second thin-film electrode layer, the dielectric layer, and the intermediate layer may have, for example, a perovskite-type crystal structure. The perovskite-type crystal structure may have an ABO3 composition or a similar ABO3 composition. xIt may have a composition of (0 < x ≤ 3). In the composition having a perovskite structure, A can be arranged at a cuboctahedral site where 12 oxygen atoms are coordinated, and B can be arranged at an octahedral site where 6 oxygen atoms are coordinated. The dielectric layer includes, for example, a ternary oxide (ABO3) having a perovskite crystal structure composed of a divalent A cation and a tetravalent B cation. The ternary oxide included in the dielectric layer is, for example, SrTiO3, CaTiO3, BaTiO3, SrHfO3, SrZrO3, PbTiO3, etc. The oxides included in the dielectric layer are not limited to these, and perovskite ternary oxides containing other cations are also possible.

[0054] The first anionized layer is, for example, [B1O2] a- It can be represented by. B1 is, for example, a monovalent cation, a divalent cation, or a trivalent cation with an atomic weight of 20 or more or an atomic weight of 40 or more, and a is 1, 2, or 3. By including such a first anionized layer in the capacitor, the leakage current of the capacitor can be more effectively suppressed. B1 included in the first anionized layer can be arranged, for example, at an octahedral site where 6 oxygen atoms are coordinated in the perovskite structure.

[0055] B1 is, for example, an alkali metal element that forms a monovalent cation and includes Li, Na, K, Rb, or Cs. B1 is, for example, an alkaline earth metal element that forms a divalent cation and includes Mg, Be, Ba, or Ca. B1 is, for example, an element that forms a trivalent cation and includes Ga or In as a metal element belonging to Group 13 of the periodic table. By having such an element for B1, an increased Schottky barrier height (SBH) can be effectively induced.

[0056] If B1 is an element that forms a trivalent cation with an atomic weight of less than 20 or less than 40, the ionic size (ionic radius) of the B1 may be significantly different from that of the corresponding metal cation contained in the electrode or dielectric, which may reduce the structural stability of the intermediate layer. Therefore, the structural stability of a capacitor having an intermediate layer containing a trivalent cation with an atomic weight of less than 20 or less than 40 may be reduced.

[0057] The first anionization layer may be, for example, [GaO2] - , [InO2] - , [BeO2] 2- , [MgO2] 2- , [BaO2] 2- , [CaO2] 2- , [LiO2] 3- , [NaO2] 3- , [KO2] 3- or [RbO2] 3- The first anionization layer can be expressed as follows. When the intermediate layer includes such a first anionization layer, the leakage current of the capacitor including the intermediate layer can be more effectively suppressed. The first anionization layer can be confirmed using, for example, high-angle annular dark-field-scanning transmission electron microscopy (HAADF-STEM).

[0058] The intermediate layer may further include a second neutral layer in addition to the first anionization layer, i.e., the intermediate layer may include a first anionization layer and a second neutral layer.

[0059] The second neutral layer can be represented by, for example, [A1O]. A1 can also be, for example, a divalent cation. A1 is a cation to which 12 oxygen atoms are coordinated in the dielectric material constituting the capacitor. For example, in the case of SrTiO3, SrHfO3, or SrZrO3 dielectrics, the second neutral layer can be [SrO]; in the case of CaTiO3 dielectrics, the second neutral layer can be [CaO]; in the case of BaTiO3 dielectrics, the second neutral layer can be [BaO]; and in the case of PbTiO3 dielectrics, the second neutral layer can be [PbO]. The composition of the second neutral layer depends on the A-site material of the dielectric material used.

[0060] The intermediate layer further includes a second neutral layer, which can improve the structural stability of the first anionization layer. Furthermore, the structural similarity between the intermediate layer and the thin-film electrode layer and the dielectric layer is increased, which can improve the overall structural stability of the intermediate layer. As a result, the structural stability of the capacitor can be improved. The second neutral layer can be confirmed, for example, using HAADF-STEM.

[0061] The intermediate layer may include, for example, a first anionization layer and a second neutral layer, which may be stacked one on top of the other. The first anionization layer and the second neutral layer may be stacked sequentially along the

[0001] direction on the (001) plane of a substrate, such as a thin-film electrode layer or a dielectric layer. The stacking order of the first anionization layer and the second neutral layer may be changed or selected depending on the surface structure of the substrate, such as a thin-film electrode layer or a dielectric layer.

[0062] The first anionization layer and the second neutral layer of the intermediate layer contain different metals, and the first anionization layer and the second neutral layer contain different metals, which allows the intermediate layer to have, for example, a perovskite crystal structure.

[0063] The intermediate layer can be composed of a single compound, including a first anionized layer and a second neutral layer. The compound forming the intermediate layer is unstable in a bulk state, but can remain stable when it has a thickness of several nanometers.

[0064] The intermediate layer may contain, for example, a metal oxide having a perovskite crystal structure represented by the following Chemical Formula 1: [Chemical formula 1] [A1B1O x ] In chemical formula 1, A1 is a divalent cation, B1 is a monovalent cation, a divalent cation, or a trivalent cation with an atomic weight of 20 or greater; 2.5 <x≦3.0である。 B1 is, for example, a monovalent cation, a divalent cation, or a trivalent cation with an atomic weight of 40 or greater.

[0065] The metal oxide represented by Chemical Formula 1 is unstable in a bulk state, but can maintain stability in an intermediate layer having a thickness of several nanometers.

[0066] The intermediate layer is made of [SrGaO x ], [CaGaO x ], [BaGaO x ], [PbGaO x ], [SrInO x ], [CaInO x ], [BaInO x ], [PbInO x ], [SrBeO x ], [CaBeO x ], [BaBeO x ], [PbBeO x ], [SrMgO x ], [CaMgO x ], [BaMgO x ], [PbMgO x ], [SrBaO x ], [CaBaO x ], [PbBaO x ], [SrCaO x ], [BaCaO x ], [PbCaO x ], [SrLiO x ], [CaLiO x ], [BaLiO x ], [PbLiO x], [SrNaO x ], [CaNaO x ], [BaNaO x ], [PbNaO x ], [SrKO x ], [CaKO x ], [BaKO x ], [PbKO x ], [SrRbO x ], [CaRbO x ], [BaRbO x ] or [PbRbO x In such metal oxides, 2.5 <x≦3.0でもある。

[0067] 2A and 2B, the capacitor includes a first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer disposed between the first and second thin-film electrode layers; and an intermediate layer disposed between the first and second thin-film electrode layers and / or the second thin-film electrode layer and the dielectric layer, the intermediate layer including a second anionization layer. The first and second thin-film electrode layers, the dielectric layer, and the intermediate layer may have, for example, a perovskite crystal structure. The dielectric layer includes, for example, a ternary oxide (ABO3) having a perovskite crystal structure composed of divalent A cations and tetravalent B cations. Examples of the ternary oxide included in the dielectric layer include SrTiO3, CaTiO3, BaTiO3, SrHfO3, SrZrO3, and PbTiO3. The oxide included in the dielectric layer is not limited to these, and perovskite ternary oxides including other cations are also possible.

[0068] The second anionization layer may be, for example, [AO] - A2 can be expressed as follows. A2 can be, for example, a monovalent cation. By including such a second anionization layer in a capacitor, the leakage current of the capacitor can be more effectively suppressed. For example, A2 included in the second anionization layer can be arranged in a cuboctahedron site where 12 oxygen atoms are coordinated in the perovskite structure.

[0069] A2 is, for example, an alkali metal element that forms a monovalent cation, and includes Li, Na, K, Rb, or Cs. When A2 contains such an element, it can effectively induce an increased Schottky barrier height (SBH).

[0070] The second anionization layer may be, for example, [LiO] - , [NaO] - , [KO] - or [RbO] - The second anionization layer can be expressed as follows. When the intermediate layer includes such a second anionization layer, the leakage current of the capacitor including the intermediate layer can be more effectively suppressed. The second anionization layer can be confirmed using, for example, HAADF-STEM.

[0071] The intermediate layer may further include a third neutral layer in addition to the second anionizable layer, i.e., the intermediate layer may include a second anionizable layer and a third neutral layer.

[0072] The third neutral layer can be represented, for example, by [B2O2]. B2 is a cation to which six oxygen atoms are coordinated in the dielectric layer material, and B2 can also be, for example, a tetravalent cation. For example, in dielectric materials such as SrTiO3, CaTiO3, BaTiO3, SrHfO3, SrZrO3, and PbTiO3, B2 can also be, for example, Ti, Hf, or Zr. The third neutral layer can be represented, for example, by [TiO2], [ZrO2], or [HfO2].

[0073] The intermediate layer further includes a third neutral layer, which can improve the structural stability of the second anionization layer. Furthermore, the structural similarity between the intermediate layer and the thin-film electrode layer and the dielectric layer is increased, which can improve the overall structural stability of the intermediate layer. As a result, the structural stability of the capacitor can be improved. The third neutral layer can be confirmed, for example, using HAADF-STEM.

[0074] The intermediate layer may include, for example, a second anionization layer and a third neutral layer, which may be stacked one on top of the other. The second anionization layer and the third neutral layer may be stacked sequentially along the

[0001] direction on the (001) plane of a substrate, such as a thin-film electrode layer or a dielectric layer. The stacking order of the second anionization layer and the third neutral layer may be changed or selected depending on the surface structure of the substrate, such as a thin-film electrode layer or a dielectric layer.

[0075] The second anionization layer and the third neutral layer contained in the intermediate layer each contain a different metal, and the second anionization layer and the third neutral layer each contain a different metal, so that the intermediate layer can have, for example, a perovskite crystal structure.

[0076] The intermediate layer can be composed of a single compound, including a second anionized layer and a third neutral layer. The compound forming the intermediate layer is unstable in a bulk state, but can remain stable when it has a thickness of several nanometers.

[0077] The intermediate layer may contain, for example, a metal oxide having a perovskite crystal structure represented by the following chemical formula 2: [Chemical formula 2] [A2B2O x ] In chemical formula 2, A2 is a monovalent cation, B2 is a tetravalent cation, 2.5 <x≦3.0である。

[0078] The metal oxide represented by Chemical Formula 2 is unstable in a bulk state, but can maintain stability in an intermediate layer having a thickness of several nanometers.

[0079] The intermediate layer may be, for example, [LiTiO x ], [NaTiO x ], [KTiO x ], [RbTiO x ], [LiZrO x ], [NaZrO x ], [KZrOx ], [RbZrO x ], [LiHfO x ], [NaHfO x ], [KHfO x ] or [RbHfO x In such metal oxides, 2.5 <x≦3.0でもある。

[0080] 3A and 3B, the capacitor includes a first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer disposed between the first and second thin-film electrode layers; and an intermediate layer disposed between the first and second thin-film electrode layers and / or between the second and second thin-film electrode layers, the intermediate layer including a first neutral layer. The first and second thin-film electrode layers, the dielectric layer, and the intermediate layer may have, for example, a perovskite crystal structure. The dielectric layer includes, for example, a ternary oxide (ABO3) having a perovskite crystal structure composed of divalent A cations and tetravalent B cations. Examples of the ternary oxide included in the dielectric layer include SrTiO3, CaTiO3, BaTiO3, SrHfO3, SrZrO3, and PbTiO3. The oxide included in the dielectric layer is not limited to these, and perovskite ternary oxides including other cations are also possible.

[0081] The intermediate layer is also a first neutral layer, which may contain, for example, a metal oxide having a perovskite crystal structure represented by the following Chemical Formula 3: [Chemical formula 3] [A3B3O3] In chemical formula 3, A3 is a trivalent cation, B3 is a trivalent cation.

[0082] A3 and B3 are, for example, different metals.

[0083] The first neutral layer may comprise a metal oxide selected from, for example, [ScAlO3], [YAlO3], [LaAlO3], [CeAlO3], [PrAlO3], [NdAlO3], [SmAlO3], [DyAlO3], [ScGaO3], [YGaO3], [LaGaO3], [CeGaO3], [PrGaO3], [NdGaO3], [SmGaO3], [DyGaO3], [ScInO3], [YInO3], [LaInO3], [CeInO3], [PrInO3], [NdInO3], [SmInO3] or [DyInO3].

[0084] The compound forming the first neutral layer may also be unstable in the bulk state, but may remain stable if it has a thickness of a few nanometers.

[0085] The first neutral layer also includes a first cationized layer and a third anionized layer. By including the first cationized layer and the third anionized layer, the first neutral layer may be structurally stable. Furthermore, the structural similarity between the intermediate layer including the first neutral layer and the thin-film electrode layer and the dielectric layer may be increased, improving the overall structural stability of the intermediate layer. As a result, the structural stability of the capacitor may be improved. The third neutral layer can be confirmed using, for example, HAADF-STEM.

[0086] The first cation layer is [AO] + A3 can be represented by the formula: A3 can also be a trivalent cation. A3 contained in the first cationized layer can be arranged, for example, in a cuboctahedron site where 12 oxygen atoms are coordinated in a perovskite structure. A3 can be, for example, a metal element belonging to Group 3 of the periodic table that forms a trivalent cation, and can include Sc, Y, La, Ce, Pr, Nd, Sm, or Dy. The first cationized layer can be, for example, [ScO] + , [YO] + , [LaO] + , [CeO] + , [PrO] + , [NdO] +, [SmO] + or [DyO] + It can be expressed as:

[0087] The third anionization layer is [B3O2] - B3 can also be a trivalent cation. A3 and B3 are, for example, different metals. B3 contained in the third anionization layer can be arranged, for example, in an octahedral site where six oxygen atoms are coordinated in a perovskite structure. B3 is, for example, a metal element belonging to Group 13 of the periodic table that forms a trivalent cation, and can also include Al, Ga, or In. The third anionization layer can be, for example, [AlO2] - , [GaO2] - or [InO2] - It can be expressed as:

[0088] The first neutral layer includes a first cation layer and a third anion layer, which can effectively induce an increased Schottky barrier height (SBH).

[0089] The first cation layer and the third anion layer can be observed, for example, by HAADF-STEM.

[0090] 4A and 4B, the capacitor includes a first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer disposed between the first thin-film electrode layer and the second thin-film electrode layer; and an intermediate layer disposed between the first thin-film electrode layer and the dielectric layer and / or between the second thin-film electrode layer and the dielectric layer. The intermediate layer may include, for example, one to three unit cells, or one or two unit cells. The first thin-film electrode layer, the second thin-film electrode layer, the dielectric layer, and the intermediate layer may have, for example, a perovskite-type crystal structure. By having one to three unit cells, the intermediate layer may have an increased Schottky barrier height (SBH) while maintaining structural stability.

[0091] The thickness of the intermediate layer is, for example, 1 Å to 15 Å, 2 Å to 12 Å, or 2 Å to 10 Å. When the intermediate layer has a thickness in such a range, the intermediate layer can have an increased Schottky barrier height (SBH) while maintaining the structural stability of the intermediate layer.

[0092] In a capacitor including the intermediate layer, the Schottky barrier height (SBH) between the first thin-film electrode layer or the second thin-film electrode layer and the dielectric layer is 1.5 eV or more, or 1.8 eV or more.

[0093] For example, in a capacitor including the intermediate layer, the Schottky barrier height (SBH) between the first thin-film electrode layer or the second thin-film electrode layer and the dielectric layer is 1.5 eV to 2.5 eV, or 1.8 eV to 2.1 eV.

[0094] The intermediate layer may be formed, for example, by epitaxial growth, and therefore may have a similar or identical crystal structure and lattice constant to the thin-film electrode layer and / or the dielectric layer, which may improve interface stability.

[0095] 1A to 4B, the capacitor includes a first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer disposed between the first and second thin-film electrode layers; and an intermediate layer disposed between the first and second thin-film electrode layers and / or between the second and second thin-film electrode layers. The dielectric material contained in the dielectric layer is not particularly limited and may be any material used as a dielectric in the art. The dielectric constant of the dielectric at room temperature (25°C) at 1 kHz to 1 MHz is, for example, 50 or more, 100 or more, 250 or more, or 500 or more. The dielectric constant of the dielectric at room temperature (25°C) at 1 kHz to 1 MHz is, for example, 100,000 or less, 50,000 or less, 10,000 or less, 5,000 or less, 1,000 or less, or 500 or less. The dielectric constant of the dielectric at room temperature (25° C.) from 1 kHz to 1 MHz is 100 to 100,000, or 100 to 10,000, or 100 to 1000, or 100 to 500.

[0096] The dielectric layer may include, for example, a dielectric material having a perovskite crystal structure represented by the following chemical formula 4: [Chemical formula 4] A4B4O3 In chemical formula 4, A4 is a monovalent, divalent, or trivalent cation; B4 is a trivalent, tetravalent or pentavalent cation.

[0097] The dielectric layer may also include a dielectric selected from, for example, SrTiO3, CaTiO3, BaTiO3, SrHfO3, CaHfO3, BaHfO3, SrZrO3, CaZrO3, BaZrO3, PbTiO3, NaNbO3, NaTaO3, RbTaO3, RbNbO3, RbTaO3 or EuTiO3.

[0098] The thickness of the dielectric layer included in the capacitor is greater than 10 nm and / or less than 100 nm, for example, 10 nm to 100 nm. If the thickness of the dielectric layer is excessively increased, the capacitance per unit volume of the capacitor will decrease. On the other hand, if the thickness of the dielectric layer is excessively thin, the ratio of the dielectric constant-decreasing region at the interface will increase, thereby decreasing the capacitance per unit volume of the capacitor.

[0099] The thickness of the first thin-film electrode layer and / or the second thin-film electrode layer included in the capacitor is, for example, 10 nm to 1,000 nm, or 10 nm to 100 nm, respectively. If the thickness of the thin-film electrode layer is excessively large, the capacitance per unit volume of the capacitor decreases. Also, if the thickness of the thin-film electrode layer is excessively small and the thickness of the dielectric layer is excessively small, the ratio of the low-dielectric-constant region at the interface increases, resulting in a decrease in the capacitance per unit volume of the capacitor.

[0100] At least one of the first thin-film electrode layer and the second thin-film electrode layer included in the capacitor may have a perovskite crystal structure, which may improve the stability of the interface with the dielectric layer.

[0101] The inclusion of the intermediate layer in the capacitor increases the capacitance of the capacitor and reduces leakage current. The type of the capacitor is not particularly limited. Examples of the capacitor include a capacitor element included in a memory cell and a multilayer capacitor used in a multilayer ceramic capacitor.

[0102] 5A shows one structure of a capacitor 20 including the aforementioned intermediate layer (not shown). This structure includes an insulating substrate 100 and a pair of electrodes: a first thin-film electrode 11, a dielectric layer 12, and a second thin-film electrode 13. The first thin-film electrode 11 and the second thin-film electrode 13 function as a lower thin-film electrode and an upper thin-film electrode, respectively. The first thin-film electrode 11 and the second thin-film electrode 13 are not electrically connected, and a dielectric layer 12 is disposed between the first thin-film electrode 11 and the second thin-film electrode 13. An intermediate layer (not shown) is disposed between the first thin-film electrode 11 and the dielectric layer 12 and / or between the second thin-film electrode 13 and the dielectric layer 12.

[0103] 5B through 5D are examples of other structures of capacitor 20 that include the intermediate layer (not shown) described above.

[0104] 5B, a dielectric layer 12 is disposed so as to cover a first thin-film electrode 11 on an insulating substrate 100, and a second electrode 13 is disposed so as to cover the dielectric layer 12. An intermediate layer (not shown) is disposed between the first thin-film electrode 11 and the dielectric layer 12 and / or between the second thin-film electrode 13 and the dielectric layer 12.

[0105] 5C, a first thin-film electrode 11 and a second thin-film electrode 13 are disposed on an insulating substrate 100, with a dielectric layer 12 disposed therebetween. An intermediate layer (not shown) is disposed between the first thin-film electrode 11 and the dielectric layer 12 and / or between the second thin-film electrode 13 and the dielectric layer 12.

[0106] 5D, a dielectric layer 12 is disposed so as to cover a part of a first thin-film electrode 11 on an insulating substrate 100, and a second electrode 13 is disposed so as to cover another part of the dielectric layer 12. An intermediate layer (not shown) is disposed between the first thin-film electrode 11 and the dielectric layer 12 and / or between the second thin-film electrode 13 and the dielectric layer 12.

[0107] FIG. 6 shows the structure of a metal-insulator-metal (MIM) capacitor according to another embodiment.

[0108] Referring to FIG. 6 , an interlayer insulating film 203 is stacked on a semiconductor substrate 201, and contact plugs 205 are formed thereon to fill contact holes exposing the semiconductor substrate 201. A mold insulating film 213 is formed on the substrate having the contact plugs 205. The mold insulating film 213 has a structure in which a lower mold insulating film 207, an etch stop layer 209, and an upper mold insulating film 211 are stacked in this order on the substrate having the contact plugs 205. The etch stop layer 209 is not limited to the location shown in FIG. 6 , and may also be formed directly on the upper surfaces of the contact plugs 205 and the interlayer insulating film 203. Alternatively, the mold insulating film 213 may be formed as a double-layered mold insulating film of the lower mold insulating film 207 and the upper mold insulating film 211, or as a single mold insulating layer. The lower mold insulating film 207 and the upper mold insulating film 211 may have an etching selectivity with respect to the etch stop layer 209. For example, if the lower mold insulating layer 207 and the upper mold insulating layer 211 are formed of silicon oxide, the etch stop layer 209 may be formed of silicon nitride. The mold insulating layer 213 is patterned to form a storage node hole 215 that exposes the upper surface of the contact plug 205 and the upper surface of the adjacent interlayer insulating layer 203.

[0109] A bottom electrode film 217', i.e., a conductive film for a bottom electrode, is formed on the entire surface of the semiconductor substrate having the storage node hole 215. The bottom electrode conductive film 217' is formed of a conductive film that has excellent step coverage, little deformation during a subsequent process of forming a dielectric film, and oxidation resistance. For example, the bottom electrode conductive film 217' may be formed of at least one metal oxide film selected from strontium ruthenium oxide (SrRuO3), iridium ruthenium oxide (IrRuO3), strontium iridium oxide (SrIrO3), calcium ruthenium oxide (CaRuO3), calcium nickel oxide (CaNiO3), barium ruthenium oxide (BaRuO3), and barium strontium ruthenium oxide ((Ba,Sr)RuO3).

[0110] A buffer insulating film 219 is formed on the lower electrode film 217′, and an isolated lower electrode film 217′ and a buffer insulating film pattern (not shown) are formed in the storage node hole 215. The buffer insulating film pattern (not shown) is selectively removed to expose the inner wall of the lower electrode film 217′. A dielectric film 224, in which a lower dielectric film 219 and an upper dielectric film 223 are sequentially stacked, is formed on the entire surface of the semiconductor substrate 201 having the lower electrode film 217′. The lower dielectric film 219 and the upper dielectric film 223 may include a dielectric material. For example, the upper dielectric film 223 may be formed of a high dielectric constant film having a higher dielectric constant than the lower dielectric film 219. The lower dielectric film 219 may also be formed of a dielectric film having a larger energy band gap than the upper dielectric film 223.

[0111] For example, the lower dielectric film 219 or the upper dielectric film 223 may be formed of one metal oxide film selected from strontium titanium oxide (SrTiO3), lithium niobium oxide (LiNbO3), potassium niobium oxide (KNbO3), potassium tantalum oxide (KTaO3), barium titanium oxide (BaTiO3), sodium niobium oxide (NaNbO3), sodium tantalum oxide (NaTaO3), calcium zirconium oxide (CaZrO3), barium zirconium oxide (BaZrO3), and strontium zirconium oxide (SrZrO3).

[0112] Alternatively, although not shown in the drawings, the lower dielectric film 219 and the upper dielectric film 223 may form one dielectric film, and such a dielectric film may be formed of the aforementioned metal oxide film.

[0113] An upper electrode 225 is formed on the upper dielectric film 223, and the upper electrode 225 is also formed of a metal film having a work function greater than that of the lower electrode 217'.

[0114] The upper electrode 225 is also formed of at least one noble metal film selected from the group consisting of a Ru film, a Pt film, and an Ir film.

[0115] For example, the upper dielectric film 223 may also be formed of at least one film selected from the group consisting of a Ta2O5 film, a TiO2 film, a doped TiO2 film, and an STO film, and the lower dielectric film 219 may also be formed of at least one film selected from the group consisting of a HfO2 film, a ZrO2 film, an Al2O3 film, and a La2O3 film.

[0116] For example, the upper dielectric film 223 and the lower dielectric film 219 may be formed of a strontium-titanium oxide (SrTiO3) film.

[0117] The intermediate dielectric film 221 is interposed between the lower dielectric film 219 and the upper dielectric film 223. The lower dielectric film 219 and the upper dielectric film 223 may be formed of a crystalline or amorphous dielectric film, and the intermediate dielectric film 221 may be formed of a crystalline or amorphous dielectric film. That is, the lower dielectric film 219 may be formed of at least one film selected from the group consisting of a crystalline or amorphous HfO2 film, a ZrO2 film, an Al2O3 film, and a La2O3 film, and the intermediate dielectric film 221 may be formed of a strontium-titanium oxide (SrTiO3) film.

[0118] For example, the intermediate dielectric film 221 may be formed of at least one film selected from the group consisting of a crystalline or amorphous HfO2 film, a ZrO2 film, an Al2O3 film, a La2O3 film, a Ta2O5 film, a TiO film, a doped TiO film, and an STO film. For example, the intermediate dielectric film 221 may be formed of a strontium-titanium oxide (SrTiO3) film. The upper dielectric film 223 may be formed of at least one film selected from the group consisting of a crystalline or amorphous Ta2O5 film, a TiO film, a doped TiO film, and an STO film. By forming the intermediate dielectric film 221 from a crystalline or amorphous dielectric film, the breakdown voltage characteristics of the dielectric film 224 can be improved. For example, if the lower dielectric film 219 and the upper dielectric film 223 are formed of a dielectric film with a crystalline structure, the breakdown voltages of the lower dielectric film 219 and the upper dielectric film 223 are improved, but their leakage current characteristics are degraded. Therefore, by forming the intermediate dielectric film 221, which is a dielectric film with an amorphous structure, between the lower dielectric film 219 and the upper dielectric film 223, a capacitor with excellent electrical characteristics, such as leakage current characteristics and breakdown voltage characteristics, can be provided.

[0119] An intermediate layer (not shown) is formed between the front surface of the semiconductor substrate 201 having the lower electrode film 217′ and the dielectric film 224 in which the lower dielectric film 219, the intermediate dielectric film 221, and the upper dielectric film 223 are stacked in order.

[0120] The MIM capacitor further includes an intermediate layer (not shown), which further improves leakage current characteristics.

[0121] The MIM capacitor shown in FIG. 6 has, for example, a concave or cylindrical structure.

[0122] According to another embodiment, an electronic device includes the above-described capacitor. The electronic device includes a capacitor including an intermediate layer, thereby reducing leakage current and providing excellent device characteristics.

[0123] The electronic device may be, for example, a semiconductor device. The electronic device may be, for example, a memory device. The memory device may be, for example, a dynamic random access memory (DRAM), a flash memory, or the like.

[0124] FIG. 7 illustrates the structure of a trench capacitor type dynamic random access memory (DRAM).

[0125] 7, an isolation region is formed on a p-type semiconductor substrate 320 using a field oxide film 321, and a gate electrode 323 and source / drain impurity regions 322, 322' are formed in the isolation region. An HTO (high temperature oxide) film is formed as an interlayer insulating film 324, and a trench buffer layer is used to cap the portion where no trench is formed. Then, a portion of the source region 322 is opened, and a contact portion (not shown) is formed.

[0126] A trench is formed on the sidewall of the interlayer insulating film 324, and a sidewall oxide film 325 is formed on the entire sidewall of the trench. The sidewall oxide film 325 compensates for damage to the silicon substrate during etching to form the trench and also serves as a dielectric film between the silicon substrate and a storage electrode to be formed later. The source region 322 formed on the sidewall of the trench has a structure in which the entire sidewall of the source region 322, except for the gate-side source region 322, is exposed.

[0127] A PN junction 332 is formed on the sidewall of the source region 322 by impurity implantation, and the source region 322 is formed on the left side of the gate electrode, and the drain region 322' is formed on the right side thereof. A trench is formed in the source region 322, and the gate side of the trench directly contacts the source region 322 on the sidewall, and impurities are further implanted into the source region 322 to form the PN junction 332.

[0128] A polysilicon layer is formed as a storage electrode 326 on a portion of the interlayer insulating film 324, the exposed source region 322, and the surface of the sidewall oxide film 325 in the trench. The storage electrode 326 is formed to contact not only the source region 322 on the gate electrode 323 side but also the entire source region 322 abutting the periphery of the upper sidewall of the trench. The source region 322 formed around the upper sidewall of the trench is expanded by the implanted impurities, so that it comes into clearer contact with the storage electrode 326. An insulating film 327 is formed along the upper surface of the storage electrode 326 as a capacitor dielectric, and a polysilicon layer is formed on top of it as a plate electrode 328, completing the trench capacitor type DRAM.

[0129] In such a trench capacitor type DRAM, the aforementioned intermediate layer (not shown) is further disposed between the storage electrode 326 and the dielectric insulating film 327 .

[0130] A method for manufacturing a capacitor according to another embodiment includes the steps of providing a first thin-film electrode layer or a second thin-film electrode layer, disposing an intermediate layer on one surface of the first thin-film electrode layer or the second thin-film electrode layer by epitaxial growth, disposing a dielectric layer on the intermediate layer, and disposing another thin-film electrode layer on the dielectric layer to provide a capacitor, wherein the capacitor includes the first thin-film electrode layer; the second thin-film electrode layer; a dielectric layer disposed between the first thin-film electrode layer and the second thin-film electrode layer; and a dielectric layer disposed between the first thin-film electrode layer and the dielectric layer, and The capacitor may further include an intermediate layer disposed between the second thin-film electrode layer and the dielectric layer, the intermediate layer having the same crystalline structure as one or more of the electrode layer and the dielectric layer in contact with the intermediate layer but a different composition from them, the intermediate layer including a first anionization layer, a second anionization layer, or a first neutral layer, the first anionization layer including monovalent cations, divalent cations, or trivalent cations with an atomic weight of 20 or more, the second anionization layer including monovalent cations, and the first neutral layer including a plurality of trivalent cations. For example, the first anionization layer may include monovalent cations, divalent cations, or trivalent cations with an atomic weight of 40 or more. The inclusion of the intermediate layer in a capacitor manufactured by the above-described manufacturing method may reduce leakage current.

[0131] Referring to FIGS. 5A to 5D, first, the first thin film electrode 11 or the second thin film electrode 13 is provided.

[0132] The first thin-film electrode 11 and / or the second thin-film electrode 13 may be, for example, strontium ruthenium oxide (SrRuO3), iridium ruthenium oxide (IrRuO3), strontium iridium oxide (SrIrO3), calcium ruthenium oxide (CaRuO3), calcium nickel oxide (CaNiO3), barium ruthenium oxide (BaRuO3), barium strontium ruthenium oxide ((Ba,Sr)RuO3 Any of the materials used as electrode materials in the art can be used, including, but not limited to, iridium (Ir), iridium-ruthenium alloy (IrRu), iridium oxide (IrO2), titanium aluminum nitride (TiAlN), titanium oxide (TiO2), ruthenium (Ru), platinum (Pt), zirconium oxide (ZrO2), tin oxide (SnO2), indium tin oxide (ITO), etc. They can be used alone or mixed with each other.

[0133] At least one of the first thin-film electrode 11 and the second thin-film electrode 13 is also an oxide having a perovskite structure. For example, at least one of the first thin-film electrode 11 and / or the second thin-film electrode 13 is selected from strontium-ruthenium oxide (SrRuO3), iridium-ruthenium oxide (IrRuO3), strontium-iridium oxide (SrIrO3), calcium-ruthenium oxide (CaRuO3), calcium-nickel oxide (CaNiO3), barium-ruthenium oxide (BaRuO3), and barium-strontium-ruthenium oxide ((Ba,Sr)RuO3).

[0134] The first electrode 11 and / or the second electrode 13 are formed by depositing a metal, metal oxide, metal nitride, metal oxynitride, or alloy by an electron beam epitaxy process, a liquid phase epitaxy process, a vapor phase epitaxy process, a chemical vapor deposition process, a sputtering process, an atomic layer deposition process, a pulsed laser deposition process, etc. The first electrode 11 and the second electrode 13 have a single layer structure or a multilayer structure.

[0135] Alternatively, the first electrode 11 or the second electrode 13 may be formed by coating and drying an electrode paste containing a conductive material to form a coating film, which is then heat-treated.

[0136] This coating method does not use a vacuum process or a high-temperature process, and therefore the first electrode 11 or the second electrode 13 can be easily manufactured.

[0137] The electrode paste includes conductive material particles, an organic component, and a solvent.

[0138] The conductive material can be any material that can generally be used as an electrode. Examples of the conductive material include conductive metal oxides such as tin oxide, indium oxide, and indium tin oxide (ITO); metals such as platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, cesium, calcium, magnesium, palladium, molybdenum, amorphous silicon, and polysilicon, and alloys thereof; inorganic conductive materials such as copper iodide and copper sulfide; conductive polymers such as polythiophene, polypyrrole, polyaniline, polyethylenedioxythiophene, and polystyrene sulfonic acid, whose conductivity has been improved by doping with a complex or iodine; and carbon materials. Such conductive materials can be used alone, or multiple materials can be used in layers or as a mixture.

[0139] The conductive material is, for example, metal particles. The use of such metal particles improves the bending resistance of the capacitor, and the coercive field does not increase even when voltage is repeatedly applied. This is because the formation of irregularities on the surface of the conductive film and the placement of the dielectric layer on the irregularities create an anchor effect, improving the adhesion between the electrode and the dielectric layer. The metal particles are, for example, metal particles containing at least one of gold, silver, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, ruthenium oxide, chromium, titanium, carbon, and indium.

[0140] The organic component and the solvent may be the same as those used for the dielectric layer.

[0141] Next, an intermediate layer (not shown) is disposed on one surface of the first thin-film electrode 11 or the second thin-film electrode 13 by epitaxial growth.

[0142] The intermediate layer may be the first anionization layer, the second anionization layer, or the first neutral layer. For more details regarding the intermediate layer, please refer to the capacitor section.

[0143] The epitaxial growth can be performed using, for example, a molecular beam epitaxial process, a liquid phase epitaxial process, a vapor phase epitaxial process, or the like.

[0144] When forming an intermediate layer (not shown) using a molecular beam epitaxy process, for example, the insulating substrate 100 on which the surface-treated first thin-film electrode 11 is formed is loaded into a reaction chamber, and the first thin-film electrode 11 is maintained at a temperature of about 400° C. to about 800° C., and the oxidant partial pressure in the chamber, for example, the oxygen partial pressure, is maintained at 10 -8 Torr to 10 -5 The pressure was maintained at Torr. The metal constituting the intermediate layer was supplied by sublimation from the metal precursor. Next, the gaseous metal was introduced onto the surface-treated first thin-film electrode 11, and then an oxidizing agent was supplied to form an intermediate layer (not shown) on the surface-treated first thin-film electrode 11. The intermediate layer (not shown) was [GaO2] - When the metal precursor is gallium or a first precursor compound containing gallium, the oxidizing agent may be oxygen (O), ozone (O), nitrogen dioxide (NO), or nitrous oxide (NO), for example, oxygen.

[0145] Next, the dielectric layer 12 is disposed on the intermediate layer (not shown).

[0146] The dielectric layer 12 may be selected from, for example, strontium titanium oxide (SrTiO3), lithium niobium oxide (LiNbO3), potassium niobium oxide (KNbO3), potassium tantalum oxide (KTaO3), barium titanium oxide (BaTiO3), calcium titanium oxide (CaTiO3), lead titanium oxide (PbTiO3), sodium niobium oxide (NaNbO3), sodium tantalum oxide (NaTaO3), calcium zirconium oxide (CaZrO3), barium zirconium oxide (BaZrO3), and strontium zirconium oxide (SrZrO3).

[0147] The dielectric layer 12 may also be an oxide having a perovskite structure, for example, strontium titanium oxide (SrTiO3).

[0148] The dielectric layer 12 may be formed using, for example, a chemical vapor deposition process, a metal organic chemical vapor deposition process, a molecular beam epitaxy process, a vapor phase epitaxy process, a liquid phase epitaxy process, a sol-gel process, a sputtering process, a pulsed laser deposition process, an atomic layer deposition process, or the like.

[0149] When the dielectric layer 12 is formed using a molecular beam epitaxy process, for example, the insulating substrate 100 on which the surface-treated first thin-film electrode 11 is formed is loaded into a reaction chamber, and the first thin-film electrode 11 is maintained at a temperature of about 400° C. to about 800° C., and the oxidant partial pressure in the chamber, for example, the oxygen partial pressure, is maintained at 10 -8 Torr to 10 -5The pressure is maintained at Torr. A metal is evaporated from a metal precursor to provide a vapor-phase metal that constitutes the intermediate layer. The vapor-phase metal is then introduced onto the surface-treated first thin-film electrode 11, and an oxidizing agent is then supplied to form an intermediate layer (not shown) on the surface-treated first thin-film electrode 11. When the dielectric layer 12 includes a SrTiO layer, the first metal precursor is composed of strontium or a first precursor compound containing strontium, titanium or a second precursor compound containing titanium, and the oxidizing agent includes oxygen (O), ozone (O), nitrogen dioxide (NO), nitrous oxide (NO), or the like. The oxidizing agent is, for example, oxygen.

[0150] When forming the dielectric layer 12 using a chemical vapor deposition process, the insulating substrate 100 having the surface-treated first thin film electrode 11 formed thereon is loaded into a reaction chamber, and the reaction chamber is maintained at a temperature of about 500°C to about 600°C and a pressure of about 1 Torr to about 10 Torr. Next, an organometallic precursor is introduced onto the surface-treated first electrode 11, and an oxidizing agent is supplied to form the dielectric layer 12 on the surface-treated first electrode 11. When the dielectric layer 12 includes SrTiO3, the organometallic precursor is composed of strontium or a first precursor compound containing strontium, and titanium or a second precursor compound containing titanium, and the oxidizing agent includes oxygen (O2), ozone (O3), nitrogen dioxide (NO2), nitrous oxide (NO), or the like.

[0151] The dielectric layer 12 may be subjected to a heat treatment process to further crystallize the material constituting the dielectric layer 12. For example, the dielectric layer 12 may be heat-treated by rapid thermal processing (RTP) in an atmosphere of oxygen (O) gas, nitrogen (N), argon (Ar), ammonia (NH), or a mixture thereof. The rapid thermal processing may be performed at a temperature of about 500° C. to about 650° C. for about 30 seconds to about 3 minutes.

[0152] Alternatively, the dielectric layer 12 may be formed by coating a dielectric paste containing the above-mentioned dielectric material, drying the resulting coating, and then heat treating the resulting coating.

[0153] This coating method does not use a vacuum process or a high-temperature process, and therefore the dielectric layer 12 can be easily manufactured.

[0154] The dielectric paste includes the above-mentioned dielectric, an organic component, and a solvent. The dielectric paste includes dielectric particles. The organic component fills the gaps between the dielectric particles to prevent short circuits in the capacitor and improve the production yield of the capacitor.

[0155] The organic component may be, for example, a monomer, an oligomer, a polymer, a photopolymerization initiator, a plasticizer, a leveling agent, a surfactant, a silane coupling agent, an antifoaming agent, a pigment, or a dispersant. From the viewpoint of improving the bending resistance of the capacitor, the organic component may be, for example, an oligomer or a polymer. The oligomer or the polymer may be, for example, a thermoplastic resin or a thermosetting resin. Examples of the organic component include an acrylic resin, an epoxy resin, a novolac resin, a phenolic resin, a polyimide precursor resin, a polyimide resin, a polysiloxane resin, a fluorine-based resin, and a polyvinyl acetal resin.

[0156] The solvent can be any solvent that disperses the dielectric particles and dissolves the organic components, such as ketone solvents like methyl ethyl ketone, acetone, diethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, cyclopentanone, and cyclohexanone; alcohol solvents like methanol, ethanol, isopropanol, isobutyl alcohol, benzyl alcohol, methoxymethylbutanol, ethylene glycol, diethylene glycol, and glycerin; ether solvents like diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, anisole, diethylene glycol dimethyl ether (diglyme), and diethylene glycol ethyl ether (carbitol); cellosolve solvents like methyl cellosolve, ethyl cellosolve, and phenyl cellosolve; and aliphatic hydrocarbon solvents like hexane, pentane, heptane, and cyclohexane. aromatic hydrocarbon solvents such as toluene, xylene, and benzene; aromatic heterocyclic compound solvents such as pyridine, pyrazine, furan, pyrrole, thiophene, and N-methylpyrrolidone; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; halogen compound solvents such as trichloroethylene, dichloromethane, chloroform, 1,2-dichloroethane, and chlorobenzene; ester solvents such as ethyl acetate, methyl acetate, ethyl formate, ethyl lactate, dimethyl carbonate, diethyl carbonate, propylene carbonate, and γ-butyrolactone; sulfur compound solvents such as dimethyl sulfoxide and sulfolane; nitrile solvents such as acetonitrile, propionitrile, and acrylonitrile; and organic acid solvents such as formic acid, acetic acid, trichloroacetic acid, and trifluoroacetic acid, or mixed solvents containing any of these.

[0157] Examples of coating methods include spin coating, blade coating, slit die coating, screen printing, bar coater, mold printing, gravure printing, flexographic printing, offset printing, dip printing, inkjet printing, dispenser method, etc. Among these coating methods, from the viewpoints of pattern processability and film removability, for example, screen printing, gravure printing, flexographic printing, offset printing, inkjet method, and dispenser method are used.

[0158] The solvent can be removed from the coating film by, for example, heat drying using an oven, a hot plate, infrared rays, or vacuum drying, which is carried out at a temperature in the range of 50° C. to 140° C. for 1 minute to several hours.

[0159] Next, the coating film is cured to improve its dielectric properties. The curing temperature is selected depending on the type of dielectric compound, the solvent used, and the type of substrate. For example, if the organic component in the dielectric paste is an acrylic resin, the curing temperature is in the range of 50°C to 300°C from the viewpoint of heat resistance. Furthermore, if the insulating substrate is polyethylene terephthalate, the curing temperature is preferably in the range of 50°C to 150°C from the viewpoint of preventing a decrease in processing precision due to thermal expansion of the substrate. Curing methods include heat curing using an oven, inert oven, hot plate, infrared rays, etc., vacuum curing, curing using a xenon flash lamp, and photocuring using UV light.

[0160] In order to improve the flatness of the dielectric layer, a planarizing layer can be formed on the coating film obtained by coating and drying a dielectric paste. The material for the planarizing layer is a known resin, such as a polyimide resin, a polysiloxane resin, an acrylic resin, or an epoxy resin. The thickness of the planarizing layer is thinner than that of the dielectric layer, for example, in terms of dielectric properties.

[0161] The dielectric layer may be patterned or unpatterned. Patterning is possible from the viewpoint of preventing misreading by reducing crosstalk between dielectric elements. For example, in terms of microfabrication, photolithography processing is used as the patterning method, in which the organic component contains a photosensitive organic component. By using photolithography processing, high integration of dielectric elements is possible.

[0162] Another thin film electrode layer is then deposited on the dielectric layer 12 to provide the capacitor 20 .

[0163] The method for disposing the other thin-film electrode layers is the same as the method for disposing the first thin-film electrode 11 or the second thin-film electrode 13.

[0164] First, when the first thin-film electrode 11 is arranged, the second thin-film electrode 13 is arranged on the dielectric layer 12, and when the second thin-film electrode 13 is arranged first, the first thin-film electrode 11 is arranged on the dielectric layer 12.

[0165] The capacitor 20 is prepared by disposing the second thin-film electrode 13 or the first thin-film electrode 11 on the dielectric layer 12 .

[0166] 8 illustrates a memory device 1200 including a layer structure according to an example embodiment. The memory device 1200 may be, for example, a non-volatile ferroelectric memory device (e.g., FRAM (ferroelectric random access memory)).

[0167] 8, the memory device 1200 may include a substrate 1210, a first doping region 1220 and a second doping region 1230 formed in the substrate 1210, a gate stack 1240, a conductive plug 1260, a data storage element 1270, and an interlayer insulating film 1250. The substrate 1210 may include a semiconductor substrate. The first doping region 1220 and the second doping region 1230 are separated from each other. The first doping region 1220 and the second doping region 1230 may be formed by doping predetermined regions of the substrate 1210 with P-type conductive impurities or N-type conductive impurities. For example, if the substrate 1210 is a P-type semiconductor substrate, the first doping region 1220 and the second doping region 1230 may also be regions doped with N-type conductive impurities. One of the first doping region 1220 and the second doping region 1230 may be a source region, and the other may be a drain region.

[0168] A gate stack 1240 is formed on the substrate 1210 between the first doping region 1220 and the second doping region 1230. The gate stack 1240 also includes a gate insulating layer and a gate electrode, which are stacked in sequence. The gate stack 1240, the first doping region 1220, and the second doping region 1230 may form a transistor.

[0169] The interlayer insulating film 1250 is formed to cover the transistor. The upper surface of the interlayer insulating film 1250 is flat. For example, the interlayer insulating film 1250 may include, but is not limited to, a silicon oxide film. A via hole H1 exposing the second doping region 1230 is formed in the interlayer insulating film 1250. The via hole H1 may be located on the second doping region 1230. A conductive plug 1260 is also included in the via hole H1. For example, the via hole H1 may be completely filled with the conductive plug 1260. One surface (e.g., bottom surface) of the conductive plug 1260 directly contacts the second doping region 1230.

[0170] A capacitor 20, which is a data storage element, may be provided on the interlayer insulating film 1250 to cover the via hole H1 and the conductive plug 1260. The capacitor 20 may be in direct contact with the conductive plug 1260. The data storage element may also include a lower electrode 11, a dielectric layer 12, and an upper electrode 13. The capacitor 20 including the sequentially stacked lower electrode 11, dielectric layer 12, and upper electrode 13 may also be the capacitor 20, first thin-film electrode 11, dielectric layer 12, and second thin-film electrode 13 shown in FIGS. 5A to 5D, respectively. In an illustrative embodiment, the gate insulating film may also include the dielectric layer 12.

[0171] However, memory device 1200 is not limited thereto. For example, in some embodiments, capacitor 20 may be directly coupled to a transistor, and / or capacitor 20 and transistor may share a doped region (e.g., second doped region 1230).

[0172] Referring to FIG. 9, a semiconductor device D10 may have a structure in which a plurality of capacitors 20 and a plurality of field effect transistors are repeatedly arranged.

[0173] 9, a semiconductor device D10 includes a field-effect transistor including a gate stack 1240 and a substrate 1210 having a source, a drain, and a channel; a contact structure 1230 arranged on the substrate 1210 without overlapping the gate stack 1240; and a capacitor 20 disposed on the contact structure 1230. The semiconductor device D10 further includes a bit line structure 930 that electrically connects the field-effect transistors to each other. While FIG. 9 illustrates the semiconductor device D10 in which the contact structures 1230 and the capacitors 20 are repeatedly arranged in the X and Y directions, this is a non-limiting example. For example, the contact structures 1230 may also be arranged in the X and Y directions, and the capacitors 20 may also be arranged in a hexagonal shape, such as a honeycomb structure.

[0174] 10 and 11 are conceptual diagrams that schematically illustrate electronic device architectures that can be applied to electronic devices according to embodiments of the present invention.

[0175] Referring to FIG. 10 , the electronic device architecture 3000 also includes a memory unit 3010, an arithmetic logic unit (ALU) 3020, and a control unit 3030. The memory unit 3010, the ALU 3020, and the control unit 3030 may be electrically coupled to one another. For example, the electronic device architecture 3000 may be embodied by a single chip including the memory unit 3010, the ALU 3020, and / or the control unit 3030. For example, the memory unit 3010, the ALU 3020, and the control unit 3030 may be coupled to one another via metal lines on the chip and communicate directly. The memory unit 3010, the ALU 3020, and / or the control unit 3030 may be monolithically integrated on a single substrate to form a single chip. The input / output device 2000 is also coupled to the electronic device architecture (chip) 3000. The control unit 3030 may be a processing circuit, such as hardware including logic circuits; a hardware / software combination, such as a processor executing software; or a combination thereof. For example, the processing circuit may more specifically include a central processing unit (CPU), an arithmetic logic unit (ALU), a digital signal processor, a microcomputer, a field programmable gate array (FPGA), a programmable logic unit, a microprocessor, an application-specific integrated circuit (ASIC), etc. Similarly, while the electronic device architecture 3000 is illustrated as including an ALU 3020, the electronic device architecture 3000 is not limited thereto and may include additional and / or alternative processing circuits. The memory unit 3010 may include a main memory and a cache memory. The electronic device architecture (chip) 3000 may also be an on-chip memory processing unit. The memory unit 3010, the ALU 3020, and / or the control unit 3030 may each independently include the layer structure described above.

[0176] Referring to FIG. 11, the cache memory 1510, ALU 1520, and control unit 1530 constitute the CPU 1500, and the cache memory 1510 also includes SRAM (static random access memory). The main memory 1600 and the auxiliary storage device 1700 are provided separately from the CPU 1500. The main memory 1600 also includes DRAM (dynamic random access memory) having the layer structure as described above. The input / output device 2500 can also be connected to the CPU 1500.

[0177] In some cases, the electronic device architecture is also embodied in a form in which a single-chip unit computer device and a unit memory device are adjacent to each other without a subunit.

[0178] The present invention will be described in more detail through the following examples and comparative examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.

[0179] (Manufacture of Dielectric) Example 1: [GaO 2 ] - First anionization layer: 1 unit cell On the (001) plane of the SrRuO3 first thin film electrode with a thickness of 100 Å, using a molecular beam epitaxial process, in the

[0001] direction, [GaO2] - The first anionized layer and the [SrO] second neutral layer were sequentially grown to form an intermediate layer.

[0180] The intermediate layer is SrGaO as a compound x (2.5 < x ≦ 3.0). The thickness of the intermediate layer including one unit cell was 4.0 Å. The molecular beam epitaxial process was performed at an oxygen partial pressure of 5×10 -8 to 8×10 -8 Torr, and the temperature of the first thin film electrode was 700 °C.

[0181] SrGaO xA SrTiO3 dielectric layer was grown on the intermediate layer to a thickness of 100 Å using the same method.

[0182] A second thin film electrode of SrRuO3 with a thickness of 200 Å was disposed on the SrTiO3 dielectric layer in the same manner to fabricate a capacitor.

[0183] Example 2: [InO 2 ] - First anionization layer: 1 unit cell [GaO2] - Instead of an anionization layer, [InO2] - A capacitor was manufactured in the same manner as in Example 1, except that an anionization layer was formed.

[0184] Example 3: [BeO 2 ] 2- First anionization layer: 1 unit cell [GaO2] - Instead of the anionized layer, [BeO2] 2- A capacitor was manufactured in the same manner as in Example 1, except that an anionization layer was formed.

[0185] Example 4: [MgO 2 ] 2- First anionization layer: 1 unit cell [GaO2] - Instead of the anionized layer, [MgO2] 2- A capacitor was manufactured in the same manner as in Example 1, except that an anionization layer was formed.

[0186] Example 5: [LiO 2 ] 3- First anionization layer: 1 unit cell [GaO2] - Instead of the anionized layer, [LiO2] 3- A capacitor was manufactured in the same manner as in Example 1, except that an anionization layer was formed.

[0187] Example 6: [LiO] - Second anionization layer: 1 unit cell On the (001) plane of the SrRuO3 first thin film electrode with a thickness of 100 Å, using the molecular beam epitaxial process, in the

[0001] direction, [LiO] - The second anionized layer and the [TiO2] third neutral layer were sequentially grown to form an intermediate layer.

[0188] This intermediate layer is, as a compound, LiTiO x (2.5 < x ≤ 3.0). The thickness of the intermediate layer containing 1 unit cell was 4.0 Å. The molecular beam epitaxial process was carried out at an oxygen partial pressure of 5×10 -8 to 8×10 -8 Torr, and the temperature of the first thin film electrode was 700 °C.

[0189] LiTiO x On the intermediate layer, in the same manner, a SrTiO3 dielectric layer was grown to a thickness of 100 Å.

[0190] On the SrTiO3 dielectric layer, in the same manner, a SrRuO3 second thin film electrode with a thickness of 100 Å was disposed to manufacture a capacitor.

[0191] Example 7: [NaO] - Second anionization layer: 1 unit cell [LiO] - Except that [NaO] was used to form the anionized layer instead of [LiO], a capacitor was manufactured in the same manner as in Example 6. - Except that [KO] was used to form the anionized layer instead of [LiO], a capacitor was manufactured in the same manner as in Example 6.

[0192] Example 8: [KO] - Second anionization layer: 1 unit cell [LiO] - Except that [KO] was used to form the anionized layer instead of [LiO], a capacitor was manufactured in the same manner as in Example 6. - Except that [KO] was used to form the anionized layer instead of [LiO], a capacitor was manufactured in the same manner as in Example 6.

[0193] Example 9: [RbO] - Second anionization layer: 1 unit cell [LiO]- Instead of the anionized layer, [RbO] - A capacitor was manufactured in the same manner as in Example 6, except that an anionization layer was formed.

[0194] Example 10: [ScO] + The first cation layer and [GaO 2 ] - Third anionization layer: 1 unit cell 100Å thick SrRuO 3 On the (001) surface of the first thin film electrode, [ScO] was grown in the

[0001] direction using a molecular beam epitaxy process. + The first cation layer and [GaO2] - A third anionization layer was subsequently grown to form the intermediate layer.

[0195] The intermediate layer is a perovskite compound, represented by ScGaO3. The thickness of the intermediate layer containing one unit cell is 4.0 Å. The molecular beam epitaxy process is performed at 5×10 -8 or 8 x 10 -8 The process was carried out at an oxygen partial pressure of 1 Torr, and the temperature of the first thin film electrode was 700°C.

[0196] A SrTiO3 dielectric layer was grown to a thickness of 100 Å on the ScGaO3 intermediate layer by the same method.

[0197] A second thin film electrode of SrRuO3 with a thickness of 100 Å was formed on the SrTiO3 dielectric layer by the same method, and a capacitor was fabricated.

[0198] Example 11: [LaO] + The first cation layer and [AlO 2 ] - Third anionization layer: 1 unit cell On the (001) face of the first SrRuO3 thin film electrode with a thickness of 100 Å, [LaO] was grown in the

[0001] direction using a molecular beam epitaxy process. + The first cation layer and [AlO2] - Anionized layers were grown sequentially to form the intermediate layer.

[0199] The intermediate layer is a perovskite compound and is represented by LaAlO3. The thickness of the intermediate layer containing 1 unit cell was 4.0 Å. The molecular beam epitaxial process was carried out at an oxygen partial pressure of 5×10 -8 to 8×10 -8 Torr, and the temperature of the electrode was 700 °C.

[0200] On the LaAlO3 intermediate layer, a SrTiO 3 dielectric layer was grown to a thickness of 100 Å. On the SrTiO3 dielectric layer, a SrRuO3 second thin film electrode with a thickness of 100 Å was disposed by the same method to fabricate a capacitor.

[0201] Example 12: [GaO 2 ] - First anionization layer: 2 unit cells SrGaO x A capacitor was fabricated in the same manner as in Example 1, except that the thickness of the intermediate layer was changed to 2 unit cells.

[0202] Comparative example 1: [LaO] + First cation layer: 1 unit cell Using the molecular beam epitaxial process on the (001) plane of the SrRuO3 first thin film electrode with a thickness of 100 Å, a [LaO] + first cationized layer and a [TiO2] third neutral layer were sequentially grown to form an intermediate layer.

[0203] The intermediate layer is a compound and is represented by LaTiO x (2.5 < x ≤ 3.0). The thickness of the intermediate layer containing 1 unit cell was 4.0 Å. The molecular beam epitaxial process was carried out at an oxygen partial pressure of 5×10 -8 to 8×10 -8 Torr, and the temperature of the first thin film electrode was 700 °C.

[0204] LaTiO x On the intermediate layer, a SrTiO3 dielectric layer was grown to a thickness of 100 Å by the same method.

[0205] A second thin film electrode of SrRuO3 with a thickness of 100 Å was formed on the SrTiO3 dielectric layer by the same method, and a capacitor was fabricated.

[0206] Comparative Example 2: [YO] + First cation layer: 1 unit cell [LaO] + Instead of the positive ionization layer, [YO] + A capacitor was manufactured in the same manner as in Comparative Example 1, except that a cationized layer was formed.

[0207] Comparative Example 3: [YO] + First cation layer: 2 unit cells A capacitor was fabricated in the same manner as in Comparative Example 2, except that the thickness of the intermediate layer was increased to two unit cells.

[0208] Comparative Example 4: Intermediate layer free: 1 unit cell A capacitor was fabricated in the same manner as in Example 1, except that the step of providing the intermediate layer was omitted.

[0209] Evaluation example 1: Schottky barrier height (SBH) calculation: first anionization layer In comparison with a laminate of SrRuO3 (electrode) / SrTiO3 (dielectric), the change (ΔV) in Schottky barrier height (SBH) of a laminate in which a first anionization layer is disposed as an intermediate layer between SrRuO3 / SrTiO3 was calculated, and some of the results are shown in Table 1 below.

[0210] 1A and 1B, a first anionization layer is disposed between SrRuO3 and SrTiO3 as an intermediate layer. The metal cations contained in the intermediate layer are located at octahedral sites in the perovskite structure where six oxygen atoms are coordinated. This corresponds to B in ABO3.

[0211] The dielectric constants and band gaps were calculated in the density functional theory (DFT) framework using the Vienna Ab initio Simulation Package (VASP).

[0212] The Schottky barrier height of the laminate including the intermediate layer is expressed by the following formula 1. The tolerance factor (t: Goldschmidt tolerance factor) is a parameter that indicates the stability of the cubic perovskite structure. The closer the factor is to 1, the higher the structural stability of the cubic perovskite, and is expressed by the following formula 2.

[0213] [Formula 1] SBH=Φ-χ+ΔV

[0214] In Equation 1, Φ is the work function of the electrode, χ is the electron affinity of the dielectric, and ΔV is the amount of change in SBH.

[0215]

number

[0216] In Equation 2, r A is the ionic radius of the A ion, and r B is the ionic radius of the B ion, and r O is the ionic radius of oxygen, and t is the Goldschmidt tolerance factor.

[0217] [Table 1]

[0218] As can be seen from Table 1, by disposing the first anionization layer as an intermediate layer between the electrode and the dielectric layer, it was confirmed that the Schottky barrier height of the stack including the intermediate layer having a cubic perovskite structure with a stable tolerance factor in the range of 0.9 to 1.10 was increased.

[0219] Such an increase in Schottky barrier height is believed to be due to the first anionization layer inducing shielding charges of opposite polarity on the corresponding electrode side, thereby inducing an additional electrostatic potential difference between the electrode and the dielectric layer.

[0220] Therefore, it was confirmed that the first anionization layer disposed as an intermediate layer between the electrode and the dielectric layer is suitable as a leakage current blocking layer for the capacitor.

[0221] Evaluation example 2: Schottky barrier height (SBH) calculation: second anionization layer In comparison with a laminate of SrRuO3 (electrode) / SrTiO3 (dielectric), the change (ΔV) in Schottky barrier height (SBH) of a laminate in which a second anionization layer is disposed as an intermediate layer between SrRuO3 / SrTiO3 was calculated, and some of the results are shown in Table 2 below.

[0222] 2A and 2B, a second anionization layer is disposed between SrRuO3 and SrTiO3 as an intermediate layer. The metal cations contained in the intermediate layer are located at cuboctahedral sites in the perovskite structure, where 12 oxygen atoms are coordinated. This corresponds to A in ABO3. The dielectric constant and band gap were calculated based on density functional theory (DFT) using the Vienna Ab initio Simulation Package (VASP).

[0223] The Schottky barrier height of the laminate including the intermediate layer is expressed by the following formula 1. The tolerance factor (t: Goldschmidt tolerance factor) is a parameter that indicates the stability of the cubic perovskite structure. The closer the tolerance factor is to 1, the higher the structural stability of the cubic perovskite, and is expressed by the following formula 2.

[0224] [Formula 1] SBH=Φ-χ+ΔV

[0225] In Equation 1, Φ is the work function of the electrode, χ is the electron affinity of the dielectric, and ΔV is the amount of change in SBH.

[0226]

number

[0227] In Equation 2, r A is the ionic radius of the A ion, and r B is the ionic radius of the B ion, and r O is the ionic radius of oxygen, and t is the Goldschmidt tolerance factor.

[0228] [Table 2]

[0229] As can be seen from Table 2, by disposing the second anionization layer between the electrode and the dielectric layer as an intermediate layer to which monovalent cations are applied, it was confirmed that the Schottky barrier height of the stack was almost increased and the cubic perovskite structure was stabilized with a tolerance factor close to 1.

[0230] Therefore, it was confirmed that the second anionization layer disposed as an intermediate layer between the electrode and the dielectric layer is suitable as a leakage current blocking layer for the capacitor.

[0231] In contrast, when a cation layer was disposed as an intermediate layer between the electrode and the dielectric layer, the Schottky barrier height of the stack was actually reduced.

[0232] Evaluation example 3: Schottky barrier height (SBH) calculation: first neutral layer In comparison with a laminate of SrRuO3 (electrode) / SrTiO3 (dielectric), the change (ΔV) in Schottky barrier height (SBH) of a laminate in which a first neutral layer is disposed as an intermediate layer between SrRuO3 / SrTiO3 was calculated, and some of the results are shown in Table 3 below.

[0233] 3A and 3B, a first neutral layer is disposed between SrRuO3 and SrTiO3 as an intermediate layer. The first neutral layer is a perovskite compound with an ABO3 composition.

[0234] The dielectric constants and band gaps were calculated on the basis of density functional theory (DFT) using the Vienna Ab initio Simulation Package (VASP).

[0235] The Schottky barrier height of the stacked body including the intermediate layer is expressed by the following formula 1. [Formula 1] SBH=Φ-χ+ΔV

[0236] In Equation 1, Φ is the work function of the electrode, χ is the electron affinity of the dielectric, and ΔV is the amount of change in SBH.

[0237] [Table 3]

[0238] As can be seen from Table 3, the Schottky barrier height of the stack was increased by disposing the first neutral layer as an intermediate layer between the electrode and the dielectric layer.

[0239] Therefore, it was confirmed that the first neutral layer disposed as an intermediate layer between the electrode and the dielectric layer is suitable as a leakage current blocking layer for the capacitor.

[0240] Evaluation example 4: Schottky barrier height (SBH) calculation: thickness change In comparison with a stack of SrRuO3 (electrode) / SrTiO3 (dielectric), a stack in which a first anionization layer or a cationization layer is disposed as an intermediate layer between the SrRuO3 / SrTiO3 was used. The change in Schottky barrier height (SBH) (ΔV) depending on the thickness of the intermediate layer was calculated, and some of the results are shown in Table 4 below. Referring to Figures 4A and 4B, a first anionization layer is disposed as an intermediate layer between the SrRuO3 / SrTiO3. The thickness of the intermediate layer is 1 unit cell and 2 unit cells.

[0241] The dielectric constants and band gaps were calculated on the basis of density functional theory (DFT) using the Vienna Ab initio Simulation Package (VASP).

[0242] The Schottky barrier height of the laminate including the intermediate layer is expressed by the following formula 1.

[0243] [Formula 1] SBH=Φ-χ+ΔV

[0244] In Equation 1, Φ is the work function of the electrode, χ is the electron affinity of the dielectric, and ΔV is the amount of change in SBH.

[0245] [Table 4]

[0246] As can be seen from Table 4, in the stack in which the first anionization layer was disposed as the intermediate layer, the Schottky barrier height of the stack increased as the thickness of the intermediate layer increased.

[0247] Therefore, it was confirmed that by increasing the thickness of the first anionization layer disposed in the intermediate layer disposed between the electrode and the dielectric layer, the intermediate layer becomes suitable as a leakage current blocking layer for the capacitor.

[0248] In contrast, in a stack in which a cationization layer was disposed as the intermediate layer, the Schottky barrier height of the stack decreased as the thickness of the intermediate layer increased.

[0249] Evaluation example 5: Leakage current measurement The leakage current of the capacitors manufactured in Example 1, Example 12, Comparative Example 1 and Comparative Example 4 was measured.

[0250] The leakage current is the current density when a voltage of 1 V is applied to the capacitor. The measurement results are shown in Table 5 below.

[0251] [Table 5]

[0252] As can be seen from Table 5, the capacitors of the examples including the intermediate layer had reduced leakage current compared to the capacitor of Comparative Example 4 which did not include an intermediate layer and the capacitor of Comparative Example 1 which included only a cationic intermediate layer.

[0253] Therefore, it was confirmed that the capacitor including the intermediate layer is suitable for manufacturing a capacitor including a dielectric layer having a high dielectric constant. [Explanation of symbols]

[0254] 11 First electrode, first thin film electrode 12 Dielectric layer 13 Second electrode, second thin film electrode 20 Capacitor 100 Insulating substrate 201 Semiconductor substrate 203 Interlayer insulating film 205 Contact plug 207 Lower mold insulating film 209 Etching stop film 211 Upper mold insulating film 213 Mold insulating film 215 Storage Node Hall 217' Lower electrode film, conductive film for lower electrode 219 Buffer insulating film, lower dielectric film 221 Intermediate Dielectric Film 223 Upper dielectric film 224 Dielectric Film 225 Upper electrode 320 p-type semiconductor substrate 321 Field oxide 322 Source Region 322' drain region 323 Gate electrode 324 Interlayer insulating film 325 Sidewall oxide film 326 Storage Electrode 327 Insulating Film 328 Plate Electrode 332 PN junction 930 Bit Line Structure 1200 memory device 1210 board 1220 First doping region 1230 Second doping region 1240 Gate Stack 1250 Interlayer insulating film 1500 CPU 1510 cache memory 1520 ALU 1530 Control Unit 1600 main memory 1700 Auxiliary Storage Device 2000 I / O devices 2500 I / O devices 3000 Electronic Device Architecture 3010 Memory Unit 3020 ALU 3030 Control Unit

Claims

1. a first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer disposed between the first thin-film electrode layer and the second thin-film electrode layer; and an intermediate layer disposed between the first thin-film electrode layer and a dielectric layer, and / or between the second thin-film electrode layer and the dielectric layer; the intermediate layer has the same crystalline structure as one or more of the electrode layer and the dielectric layer in contact with the intermediate layer, but has a different composition from the electrode layer and the dielectric layer; the intermediate layer comprises a first neutral layer; the first neutral layer comprises a plurality of trivalent cations; The first neutral layer is [ScAlO 3 ], [YAlO 3 ], [CeAlO 3 ], [PrAlO 3 ], [NdAlO 3 ], [SmAlO 3 ], [DyAlO 3 ], [ScGaO 3 ], [YGaO 3 ], [LaGaO 3 ], [CeGaO 3 ], [PrGaO 3 ], [NdGaO 3 ], [SmGaO 3 ], [DyGaO 3 ], containing a metal oxide selected from the group consisting of [ScInO3], [YInO3], [LaInO3], [CeInO3], [PrInO3], [NdInO3], [SmInO3] and [DyInO3]; A capacitor, wherein a Schottky barrier height (SBH) between the first thin-film electrode layer or the second thin-film electrode layer and the dielectric layer is 1.5 eV or more.

2. A first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer disposed between the first thin-film electrode layer and the second thin-film electrode layer; and an intermediate layer disposed between the first thin-film electrode layer and a dielectric layer, and / or between the second thin-film electrode layer and the dielectric layer; the intermediate layer has the same crystalline structure as one or more of the electrode layer and the dielectric layer in contact with the intermediate layer, but has a different composition from the electrode layer and the dielectric layer; the intermediate layer comprises a first neutral layer; the first neutral layer comprises a plurality of trivalent cations; The first neutral layer is [A3O] ＋ a first cationized layer represented by [B3O ２ ] － and a third anionization layer represented by A3 is a trivalent cation, B3 is a trivalent cation, and A3 and B3 are different metals; A capacitor, wherein a Schottky barrier height (SBH) between the first thin-film electrode layer or the second thin-film electrode layer and the dielectric layer is 1.5 eV or more.

3. A3 is Sc, Y, La, Ce, Pr, Nd, Sm or Dy; The capacitor of claim 2 , wherein B3 is Al, Ga, or In.

4. The first neutral layer is [ScO] ＋ , [YO] ＋ , [LaO] ＋ [CeO] ＋ [PrO] ＋ [NdO] ＋ [SmO] ＋ or [DyO] ＋ a first cationized layer represented by [AlO ２ ] － , [GaO ２ ] － or [InO ２ ] － and a third anionization layer represented by:

5. the intermediate layer comprises 1 to 3 unit cells, and the thickness of the intermediate layer is 1 Å to 15 Å; The capacitor according to claim 1 or 2, wherein the intermediate layer is formed by epitaxial growth.

6. 3. The capacitor according to claim 1 or 2, wherein the dielectric layer comprises a dielectric material having a perovskite crystal structure represented by the following chemical formula 4: [Chemical formula 4] A4B4O ３ In the above Chemical Formula 4, A4 is a monovalent, divalent or trivalent cation; B4 is a trivalent, tetravalent or pentavalent cation.

7. The dielectric layer is SrTiO ３ , CaTiO ３ , BaTiO ３ , SrHfO ３ , CaHfO ３ , BaHfO ３ , SrZrO ３ , CaZrO ３ , BaZrO ３ , PbTiO ３ , NaNbO ３ , NaTaO ３ , RbTaO ３ , RbNbO ３ , RbTaO ３ or EuTiO ３ 3. The capacitor of claim 1, comprising a dielectric selected from the group consisting of:

8. The thickness of the dielectric layer is 10 nm to 100 nm, The first thin-film electrode layer and the second thin-film electrode layer each have a thickness of 10 nm to 1,000 nm; 3. The capacitor according to claim 1, wherein at least one of the first thin-film electrode layer and the second thin-film electrode layer has a perovskite crystal structure.

9. An electronic device comprising the capacitor according to claim 1 or 2.

10. The electronic device according to claim 9 , wherein the electronic device is a semiconductor device.

11. providing a first thin-film electrode layer or a second thin-film electrode layer; disposing an intermediate layer on one surface of the first thin-film electrode layer or the second thin-film electrode layer by epitaxial growth; disposing a dielectric layer on the intermediate layer; and depositing another thin film electrode layer on the dielectric layer to provide a capacitor; the capacitor comprises: a first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer disposed between the first thin-film electrode layer and the second thin-film electrode layer; and an intermediate layer disposed between the first thin-film electrode layer and a dielectric layer, and / or between the second thin-film electrode layer and the dielectric layer; the intermediate layer has the same crystalline structure as one or more of the electrode layer and the dielectric layer in contact with the intermediate layer, but has a different composition from the electrode layer and the dielectric layer; the intermediate layer comprises a first neutral layer; the first neutral layer comprises a plurality of trivalent cations; The first neutral layer is [ScAlO 3 ], [YAlO 3 ], [CeAlO 3 ], [PrAlO 3 ], [NdAlO 3 ], [SmAlO 3 ], [DyAlO 3 ], [ScGaO 3 ], [YGaO 3 ], [LaGaO 3 ], [CeGaO 3 ], [PrGaO 3 ], [NdGaO 3 ], [SmGaO 3 ], [DyGaO 3 ], containing a metal oxide selected from the group consisting of [ScInO3], [YInO3], [LaInO3], [CeInO3], [PrInO3], [NdInO3], [SmInO3] and [DyInO3]; the dielectric layer includes a ternary oxide having a perovskite crystal structure; A method for manufacturing a capacitor, wherein a Schottky barrier height (SBH) between the first thin-film electrode layer or the second thin-film electrode layer and the dielectric layer is 1.5 eV or more.

12. Providing a first thin-film electrode layer or a second thin-film electrode layer; disposing an intermediate layer on one surface of the first thin-film electrode layer or the second thin-film electrode layer by epitaxial growth; disposing a dielectric layer on the intermediate layer; and depositing another thin film electrode layer on the dielectric layer to provide a capacitor; the capacitor comprises: a first thin-film electrode layer; a second thin-film electrode layer; a dielectric layer disposed between the first thin-film electrode layer and the second thin-film electrode layer; and an intermediate layer disposed between the first thin-film electrode layer and a dielectric layer, and / or between the second thin-film electrode layer and the dielectric layer; the intermediate layer has the same crystalline structure as one or more of the electrode layer and the dielectric layer in contact with the intermediate layer, but has a different composition from the electrode layer and the dielectric layer; the intermediate layer comprises a first neutral layer; the first neutral layer comprises a plurality of trivalent cations; The first neutral layer is a first cationized layer represented by [AO] + ; a third anionization layer represented by [B3O2]-; A3 is a trivalent cation, B3 is a trivalent cation, and A3 and B3 are different metals; the dielectric layer includes a ternary oxide having a perovskite crystal structure; A method for manufacturing a capacitor, wherein a Schottky barrier height (SBH) between the first thin-film electrode layer or the second thin-film electrode layer and the dielectric layer is 1.5 eV or more.

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