Semiconductor device and method of manufacturing the same

Abstract

The present disclosure relates to a semiconductor device including a resistance change layer and a metal organic framework layer in which metal ions are embedded, and a manufacturing method thereof. The semiconductor device according to an embodiment of the present disclosure includes a first electrode, a first resistance change layer disposed on the first electrode, a conductive control layer disposed on the first resistance change layer, a second resistance change layer disposed on the conductive control layer, and a second electrode disposed on the second resistance change layer. The conductive control layer includes a metal organic framework layer and metal particles embedded in the metal organic framework layer.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to Korean Application No. 10-2022-0031717, filed with the Korean Intellectual Property Office on March 14, 2022, the entirety of which is incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to semiconductor devices including resistance-varying layers and methods for manufacturing the same. Background Technology

[0004] Generally, a resistivity-changing material refers to a material whose resistance changes when an external stimulus (such as heat, current, voltage, or light) is applied. Even after the external stimulus is removed, the resistivity-changing material retains its changed resistance. Resistivity-changing storage devices utilize the electrical properties of these materials to store signal information.

[0005] Resistance-varying memory devices can switch between low-resistance and high-resistance states via set and reset operations. Depending on the factors that cause the switching operation, resistance-varying memory devices can be classified as resistive RAM, phase-change RAM, magnetic memory, etc. Among them, resistive RAM achieves different resistance states by applying voltage or current across the resistance-varying layer to create or block low-resistance electrical paths within the layer. Summary of the Invention

[0006] A semiconductor device according to embodiments of the present disclosure may include a first electrode, a first resistance variation layer disposed on the first electrode, a conductivity control layer disposed on the first resistance variation layer, a second resistance variation layer disposed on the conductivity control layer, and a second electrode disposed on the second resistance variation layer. The conductivity control layer may include a metal-organic framework layer and metal particles embedded in the metal-organic framework layer.

[0007] A method for manufacturing a semiconductor device according to another embodiment of this disclosure is disclosed. In this method, a substrate may be provided. A first electrode may be formed on the substrate. A first resistance variation layer may be formed on the first electrode. A conductivity control layer comprising an insulating metal-organic framework layer and metal particles embedded in the metal-organic framework layer may be formed on the first resistance variation layer. A second resistance variation layer may be formed on the conductivity control layer. A second electrode may be formed on the second resistance variation layer.

[0008] A semiconductor device according to another embodiment of this disclosure may include a first conductive line and a second conductive line disposed on different planes, and a columnar structure disposed in the region where the first conductive line and the second conductive line intersect. The columnar structure may include a first resistance variation layer, a conductivity control layer, and a second resistance variation layer. The conductivity control layer may include a metal-organic framework layer and metal particles embedded in the metal-organic framework layer. Attached Figure Description

[0009] Figure 1 This is a schematic cross-sectional view of a semiconductor device according to an embodiment of the present disclosure.

[0010] Figure 2 This is a schematic plan view illustrating the conductivity control layer of a semiconductor device according to an embodiment of the present disclosure.

[0011] Figure 3 This is a perspective view schematically showing the conductivity control layer of a semiconductor device according to an embodiment of the present disclosure.

[0012] Figure 4 This is a schematic view illustrating the metal-organic framework of a semiconductor device according to an embodiment of the present disclosure.

[0013] Figures 5A to 5C This is a view schematically illustrating the operation of a semiconductor device according to an embodiment of the present disclosure.

[0014] Figure 6 This is a schematic cross-sectional view of a semiconductor device according to another embodiment of the present disclosure.

[0015] Figures 7 to 10 This is a cross-sectional view schematically illustrating a method for manufacturing a semiconductor device according to an embodiment of the present disclosure.

[0016] Figure 11A , Figure 11B , Figure 12A and Figure 12B This is a view schematically illustrating a method for forming a conductivity control layer of a semiconductor device according to an embodiment of the present disclosure.

[0017] Figure 13A This is a perspective view schematically illustrating a semiconductor device according to another embodiment of the present disclosure.

[0018] Figure 13B yes Figure 13A A partially magnified view of a semiconductor device.

[0019] Figure 14A This is a perspective view schematically illustrating a semiconductor device according to another embodiment of the present disclosure.

[0020] Figure 14B yes Figure 14A A partially magnified view of a semiconductor device. Detailed Implementation

[0021] In the following, embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. In the drawings, the sizes of the components (such as the width and thickness of the components) are enlarged to clearly illustrate the components of each device. The terms used herein may correspond to words chosen in consideration of their function in the embodiments, and the meaning of the terms may be interpreted differently by those skilled in the art to which the embodiments pertain. If a term is explicitly defined in detail, the term may be interpreted according to said definition. Unless otherwise defined, the terms used herein (including technical and scientific terms) have the same meaning as commonly understood by those skilled in the art to which the embodiments pertain.

[0022] Furthermore, unless explicitly used otherwise in the context, the singular form of a word should be understood to include the plural form of the word. It will be understood that the terms “comprising,” “including,” or “having” are intended to clearly state the presence of a feature, quantity, step, operation, component, element, part, or combination thereof, and not to exclude or add the possibility of the presence of one or more other features, quantities, steps, operations, components, elements, parts, or combinations thereof.

[0023] Furthermore, in a method of execution or manufacturing, unless a specific order is explicitly described in the context, each process constituting the method may be performed in a different order than prescribed. Each process may be performed in the same manner as stated or may be performed substantially simultaneously. In another example, at least a portion of each of the aforementioned processes may be performed in a reversed order.

[0024] Embodiments of this disclosure can provide semiconductor devices, each including a conductivity control layer disposed between a first resistance variation layer and a second resistance variation layer. The conductivity control layer may include a metal-organic framework layer and metal particles embedded in the metal-organic framework layer.

[0025] The conductive wires generated by the operating voltage within the first and second resistance-varying layers can be controlled to pass through the metal particles of the conductivity control layer. Therefore, the density and distribution of the conductive wires can be controlled by controlling the size and distribution of the metal particles.

[0026] According to embodiments of this disclosure, by controlling the density and distribution of conductive filaments passing through the conductive control layer, the uniformity of the set voltage and reset voltage required to switch the resistive state of a semiconductor device can be improved. As a result, the durability and reliability of the semiconductor device used for set and reset operations can be improved.

[0027] Figure 1 This is a schematic cross-sectional view of a semiconductor device according to an embodiment of the present disclosure. Figure 2 This is a schematic plan view illustrating the conductivity control layer of a semiconductor device according to an embodiment of the present disclosure. Figure 3 This is a perspective view schematically showing the conductivity control layer of a semiconductor device according to an embodiment of the present disclosure. Figure 4 This is a schematic view illustrating the metal-organic framework of a semiconductor device according to an embodiment of the present disclosure.

[0028] refer to Figure 1 The semiconductor device 1 may include a first electrode 110, a first resistance variation layer 120 disposed on the first electrode layer 110, a conductivity control layer 130 disposed on the first resistance variation layer 120, a second resistance variation layer 140 disposed on the conductivity control layer 130, and a second electrode 150 disposed on the second resistance variation layer 140. The first electrode 110 and the second electrode 150 may be disposed in a first direction (e.g., Figure 1 The first resistance variation layer 120 and the second resistance variation layer 140, as well as the conductivity control layer 130, are spaced apart from each other in the z-direction. The first resistance variation layer 120, the second resistance variation layer 140, and the conductivity control layer 130 can be disposed between the first electrode 110 and the second electrode 150. The conductivity control layer 130 can be disposed between the first resistance variation layer 120 and the second resistance variation layer 140. In an embodiment, the semiconductor device 1 can be a resistance variation memory device, in which the resistance of the first resistance variation layer 120 and the second resistance variation layer 140 varies according to the arrangement and shape of the conductive wires formed within the first resistance variation layer 120 and the second resistance variation layer 140.

[0029] Each of the first electrode 110 and the second electrode 150 may include a conductive material. For example, the conductive material may include a doped semiconductor, a metal, a conductive metal nitride, a conductive metal carbide, a conductive metal silicide, or a conductive metal oxide. For example, the conductive material may include n-type or p-type doped silicon (Si), tungsten (W), titanium (Ti), copper (Cu), aluminum (Al), ruthenium (Ru), platinum (Pt), iridium (Ir), iridium oxide, tungsten nitride, titanium nitride, tantalum nitride, tungsten carbide, titanium carbide, tungsten silicide, titanium silicide, tantalum silicide, ruthenium oxide, or combinations of two or more thereof. The first electrode 110 and the second electrode 150 may be made of substantially the same material. Alternatively, the first electrode 110 and the second electrode 150 may be made of different materials.

[0030] Each of the first resistance-changing layer 120 and the second resistance-changing layer 140 may include a resistance-changing material. The resistance-changing material may include metal oxides, such as titanium oxide, aluminum oxide, nickel oxide, copper oxide, zirconium oxide, manganese oxide, hafnium oxide, tungsten oxide, tantalum oxide, niobium oxide, iron oxide, etc. As another example, the resistance-changing material may include perovskite materials, such as PCMO(Pr 0.7 Ca 0.3 MnO3), LCMO(La 1-x Ca x MnO3), BSCFO(Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ ), YBCO(YBa2Cu3O) 7-x (Ba,Sr)TiO3 (doped with Cr, Nb), SrZrO3 (doped with Cr, V), (La,Sr)MnO3, Sr 1-x La x TiO3, La 1-x Sr x FeO3, La 1-x Sr x CoO3, SrFeO 2.7 Materials such as LaCoO3, RuSr2GdCu2O3, and YBa2Cu3O7. As yet another example, resistivity-changing materials can include selenide-based materials, such as Ge... x Se 1-x (Doped with Ag, Cu, Te) or metal sulfides, such as Ag2S, Cu2S, CdS, ZnS, etc.

[0031] At the same time, if reference Figures 5A to 5C The resistance of the first resistance-changing layer 120 and the second resistance-changing layer 140 can decrease when the conductive wires passing through them are formed as a result of an externally applied voltage. Alternatively, the resistance of the first resistance-changing layer 120 and the second resistance-changing layer 140 can increase again when at least a portion of the conductive wires is interrupted or disconnected by an externally applied voltage. The conductive wires may include oxygen vacancies or metals in the resistance-changing material.

[0032] The conductivity control layer 130 can control the shape, density, distribution, and arrangement of the conductive wires formed inside the first resistance change layer 120 and the second resistance change layer 140. By controlling the conductive wires, the conductivity control layer 130 can control the density of charge carriers conducted through the conductive wires.

[0033] The conductivity control layer 130 may include a metal-organic framework layer 132 and metal particles 134 embedded in the metal-organic framework layer 132. The metal-organic framework layer 132 may have electrical insulating properties, and the metal particles 134 may have conductive properties. Since the metal particles 134 are disposed inside the substantially planar metal-organic framework layer 132, the metal particles 134 may be disposed on a plane spaced at a predetermined distance from the first electrode 110 or the second electrode 150 in a first direction.

[0034] refer to Figures 1 to 3 The diameter D of the metal particle 134, or the height of the metal particle along the z-direction on the first resistance-changing layer 120, can be substantially equal to or greater than the thickness t of the metal-organic framework layer 132. The metal particle 134 can penetrate through the metal-organic framework layer 132 in the z-direction and can contact the first resistance-changing layer 120 and the second resistance-changing layer 140.

[0035] The metal-organic framework layer 132 may include at least two metal-organic frameworks. For example... Figure 3 As shown, metal-organic frameworks 132a, 132b, 132c, and 132d are stacked in the thickness direction (i.e., the z-direction). Although Figure 3 The first to fourth metal-organic frameworks 132a, 132b, 132c and 132d are shown as at least two metal-organic frameworks, but this disclosure is not necessarily limited to this, and a variety of metal-organic frameworks may be used in the metal-organic framework layer 132.

[0036] like Figure 2 and Figure 3 As shown, each of the first to fourth metal-organic frameworks 132a, 132b, 132c, and 132d may comprise a material with a two-dimensional structure having multiple cavities V. Here, a two-dimensional structure may refer to a sheet-like structure disposed on a two-dimensional plane. Figure 2 A representative metal-organic framework 132a is shown, in which cavities V can be arranged at regular intervals, and the width of each cavity V can be, for example, from one nanometer (1 nm) to 100 nm. The first to fourth metal-organic frameworks 132a, 132b, 132c, and 132d can be made of the same material. Each of the first to fourth metal-organic frameworks 132a, 132b, 132c, and 132d can have electrically insulating properties.

[0037] refer to Figure 4According to embodiments of the present disclosure, the metal-organic framework M can be a material in which metal-containing nodes Ma and organic ligands Mb are coordinated. The metal-containing nodes Ma can include, for example, metal ions or metal clusters. For example, the metal can include zinc (Zn), chromium (Cr), indium (In), gallium (Ga), copper (Cu), iron (Fe), molybdenum (Mo), cobalt (Co), ruthenium (Ru), manganese (Mn), lanthanum (La), titanium (Ti), hafnium (Hf), cadmium (Cd), zirconium (Zr), etc.

[0038] For example, organic ligand Mb may include oxalic acid, fumaric acid, benzenehexathiol, triphenylenehexathiol, 1,4-benzene dicarboxylic acid, hexaaminobenzene, tetrakis(4-carboxyphenyl)-porphyrinato-cobalt(II), tetrakis(4-carboxyphenyl)-porphyrin, etc. As another example, organic ligand Mb may include H2BDC, H2BDC-Br, H2BDC-OH, H2BDC-NO2, H2BDC-NH2, H4DOT, H2BDC-(Me)2, H2BDC-(Cl)2, etc.

[0039] Metal-organic frameworks (M) with two-dimensional structures can possess porous structures including cavities V. M can also exhibit physically and chemically stable two-dimensional network connections. Specifically, within M, coordination bonds between metal nodes Ma and organic ligands Mb can be regularly formed in two dimensions. Consequently, M can exist as sheets with nanoscale thicknesses.

[0040] Re-reference Figure 3 In the metal-organic framework layer 132, the cavities V of the first to fourth metal-organic frameworks 132a, 132b, 132c, and 132d can be arranged to overlap and align with each other in the z-direction. Metal particles 134 can be disposed within the internal space of the overlapping cavities V. Since the cavities V of the metal-organic framework layer 132 are arranged at regular intervals, the metal particles 134 can also be arranged regularly within the metal-organic framework layer 132.

[0041] Metal particles 134 can have a shape in which metal atoms are aggregated. In the middle Figure 1 , Figure 2 and Figure 3 In the figure, the metal particle 134 is shown in a spherical shape, but is not necessarily limited to this, and other three-dimensional shapes are also possible.

[0042] In embodiments, the width or diameter D of the metal particles 134 can have a size of, for example, 1 nm to 100 nm. In this case, the width or diameter D of the metal particles 134 can be substantially the same as or smaller than the width of the cavity V. For example, the metal particles 134 may include cobalt (Co), nickel (Ni), copper (Cu), iron (Fe), platinum (Pt), gold (Au), silver (Ag), iridium (Ir), ruthenium (Ru), palladium (Pd), manganese (Mn), or combinations of two or more thereof. That is, as will be described later in the manufacturing method, the width or diameter D of the metal particles 134 can be determined by the width d of the cavity V of the metal-organic framework layer 132. Therefore, the size of the metal particles 134 can be controlled or determined by controlling the width d of the cavity V of the metal-organic framework layer 132.

[0043] exist Figure 1 In this configuration, the first electrode 110 may be disposed on a substrate (not shown). The substrate may be any substrate used in semiconductor device manufacturing processes. As an example, the substrate may include a semiconductor, an insulator, or a conductor.

[0044] As described above, the semiconductor device 1 according to embodiments of the present disclosure may include a first resistance variation layer 120, a second resistance variation layer 140, and a conductivity control layer 130, which are disposed or layered between the first electrode 110 and the second electrode 150. The conductivity control layer 130 may include conductive metal particles 134 disposed in the cavity V of the insulating metal-organic framework layer 132. The metal particles 134 may be arranged to contact the first resistance variation layer 120 and the second resistance variation layer 140. During a write operation of the semiconductor device 1, the metal particles 134 may control or determine the shape, density, distribution, and arrangement of conductive filaments formed within the first resistance variation layer 120 and the second resistance variation layer 140.

[0045] Figures 5A to 5C This is a view schematically illustrating the operation of a semiconductor device according to an embodiment of the present disclosure. Figures 5A to 5C The operation of the relevant semiconductor devices will use the reference. Figure 1 The semiconductor device 1 is described.

[0046] refer to Figure 5AA first write operation can be performed in the semiconductor device 1. Specifically, the first write operation can be performed by applying a first write voltage V1, which is supplied by the power supply 10 and is equal to or greater than a predetermined threshold voltage between the first electrode 110 and the second electrode 150 of the semiconductor device 1. The first write operation can be an operation to reduce the resistance of the semiconductor device 1 by first forming a conductive filament after the semiconductor device 1 has been manufactured. That is, the first write operation can be referred to as the formation operation of the semiconductor device 1.

[0047] The method of applying the first write voltage V1 can be performed by applying a bias voltage with a first polarity (e.g., positive polarity) to the second electrode 150 while the first electrode 110 is grounded. By applying the first write voltage V1, a first conductive wire 125 and a second conductive wire 145 connecting the first electrode 110 and the second electrode 150 to each other can be formed in the first resistance variation layer 120 and the second resistance variation layer 140, respectively. With the formation of the first conductive wire 125 and the second conductive wire 145 connecting the first electrode 110 and the second electrode 150, conductive charge carriers can be conducted between the first electrode 110 and the second electrode 150 through the first conductive wire 125 and the second conductive wire 145. Therefore, the resistance of the first resistance variation layer 120 and the second resistance variation layer 140 can be reduced. Even after the first write voltage V1 is removed, the first conductive wire 125 and the second conductive wire 145 can still remain in the first resistance variation layer 120 and the second resistance variation layer 140, respectively. Therefore, each of the first resistance change layer 120 and the second resistance change layer 140 can store the state of reduced resistance (i.e., low resistance state) as the first signal information.

[0048] refer to Figure 5A When a first write voltage V1 is applied, the conductive metal particles 134 can be used to concentrate the electric field formed by the first write voltage V1 between the first resistance-changing layer 120 and the second resistance-changing layer 140. Since the metal particles 134 are arranged to contact the first resistance-changing layer 120 and the second resistance-changing layer 140, the metal particles 134 can be connected to the first conductive filament 125 generated in the first resistance-changing layer 120 and the second conductive filament 145 generated in the second resistance-changing layer 140.

[0049] As per the above reference Figures 1 to 4The metal particles 134 can be regularly arranged inside the insulating metal-organic framework layer 132, and the size of the metal particles 134 can depend on the width of the cavity V. Therefore, when performing the first write operation, the shape, density, and distribution of each of the first conductive filament 125 and the second conductive filament 145 can be controlled by the uniform distribution of the metal particles 134. Thus, the first conductive filament 125 and the second conductive filament 145 generated by the first write voltage V1 can be uniformly controlled, thereby improving the reliability of the first write operation.

[0050] refer to Figure 5B A second write operation can be performed in semiconductor device 1. Specifically, using power supply 10, the second write operation can be performed by applying a second write voltage V2 equal to or greater than a predetermined threshold voltage between the first electrode 110 and the second electrode 150. The second write operation can be an operation to remove or electrically disconnect at least a portion of each of the first conductive filament 125 and the second conductive filament 145 generated in the first resistance-changing layer 120 and the second resistance-changing layer 140 by the first write operation. That is, the second write operation can be referred to as a reset operation of semiconductor device 1.

[0051] The method of applying the second write voltage V2 can be performed by applying a bias voltage having a second polarity (e.g., negative polarity) to the second electrode 150 while the first electrode 110 is grounded. By applying the second write voltage V2, at least a portion of the first conductive filament 125 and the second conductive filament 145 can be removed. In one embodiment, at least a portion of the first conductive filament 125 and the second conductive filament 145 can be removed by oxidizing the metal constituting the first conductive filament 125 and the second conductive filament 145 with the second write voltage V2, or by removing oxygen cavities constituting the first conductive filament 125 and the second conductive filament 145 with the second write voltage V2. In another embodiment, the removal of at least a portion of the first conductive filament 125 and the second conductive filament 145 can be attributed to Joule heating generated in the first conductive filament 125 and the second conductive filament 145 by the second write voltage V2.

[0052] refer to Figure 5B As a result of the second write operation, at least a portion of the first conductive wire and the second conductive wire ( Figure 5AWires 125 and 145 are removed. The electrically disconnected first conductive wire 125c and second conductive wire 145c no longer contact the interface between the metal particle 134 and the first resistance-changing layer 120, and the metal particle 134 at the interface between the second resistance-changing layer 140 and the metal particle 134, respectively. In an embodiment, at least a portion of the second conductive wire 145c may be additionally removed at the interface between the second resistance-changing layer 140 and the second electrode 150. The first conductive wire 125c and the second conductive wire 145c may be... Figure 5B The portions not shown are electrically disconnected. As described above, by disconnecting at least a portion of the first conductive wire 125c and the second conductive wire 145c, the resistance of the first resistance changing layer 120 and the second resistance changing layer 140 can increase. After the second write voltage V2 is removed, the electrically disconnected first conductive wire 125c and the second conductive wire 145c can remain in the first resistance changing layer 120 and the second resistance changing layer 140; however, each of the first resistance changing layer 120 and the second resistance changing layer 140 can store the increased resistance state (i.e., the high resistance state) as a second signal information.

[0053] refer to Figure 5C A third write operation can be performed in semiconductor device 1. Specifically, using power supply 10, the third write operation can be performed by applying a third write voltage V3 equal to or greater than a predetermined threshold voltage between the first electrode 110 and the second electrode 150. The third write operation can be an operation to reconnect the disconnected portions of the first conductive wire 125c and the second conductive wire 145c present in the first resistance change layer 120 and the second resistance change layer 140 due to the second write operation. Figure 5C As shown, the third write operation can electrically connect the first electrode 110 and the second electrode 150 through the first conductive wire 125, the second conductive wire 145, and the metal particles 134. The third write operation can be referred to as the set operation of the semiconductor device 1. Through the set operation, the resistance of the first resistance-changing layer 120 and the second resistance-changing layer 140 can be reduced.

[0054] The third write voltage V3 can be applied to the second electrode 150 with a first polarity (e.g., positive polarity) while the first electrode 110 is grounded. The magnitude of the third voltage V3 can be less than [the value of the voltage V3]. Figure 5A The first write voltage V1.

[0055] By applying a third writing voltage V3, the first conductive wire and the second conductive wire ( Figure 5BThe disconnected portions of electrodes 125c and 145c can be restored or reformed, and the first electrode 110 and the second electrode 150 can be connected via the first conductive wire 125 and the second conductive wire 145. The first conductive wire 125 and the second conductive wire 145 can contact the metal particles 134. Even after the third write voltage V3 is removed, the first conductive wire 125 and the second conductive wire 145 can still remain in the first resistance change layer 120 and the second resistance change layer 140, respectively. Therefore, each of the first resistance change layer 120 and the second resistance change layer 140 can store the state of decreased resistance, i.e., the first signal information.

[0056] Figure 6 This is a schematic cross-sectional view illustrating a semiconductor device according to another embodiment of the present disclosure. Reference Figure 6 ,and Figure 1 Compared to semiconductor device 1, semiconductor device 2 may further include a conductivity control layer 160 and a resistance change layer 170 between the second resistance change layer 140 and the second electrode 150.

[0057] refer to Figure 6 The semiconductor device 2 may include a first resistance variation layer to a third resistance variation layer 120, 140 and 170 between the first electrode 110 and the second electrode 150. A first conductivity control layer 130 may be disposed between the first resistance variation layer 120 and the second resistance variation layer 140, and a second conductivity control layer 160 may be disposed between the second resistance variation layer 140 and the third resistance variation layer 170.

[0058] The material, structure, and electrical properties of the third resistance variation layer 170 can be compared with those of the reference. Figure 1 The first resistance variation layer 120 and the second resistance variation layer 140 are described to have essentially the same material, structure, and electrical properties. The material, structure, and electrical properties of the second conductivity control layer 160 can be the same as those of the reference layer. Figure 1 The materials, structure, and electrical properties of the described conductive control layer 130 are basically the same.

[0059] Compared to semiconductor device 1, Figure 6The semiconductor device 2 may further include a third resistance-changing layer 170. Therefore, the total thickness of the resistance-changing layers in the semiconductor device 2 (i.e., the sum of the thicknesses of the first to third resistance-changing layers 120, 140, and 170) can be greater than the total thickness of the resistance-changing layers in the semiconductor device 1 (i.e., the sum of the thicknesses of the first resistance-changing layer 120 and the second resistance-changing layer 140). Therefore, the semiconductor device 2 may further include a second conductivity control layer 160 corresponding to the increased overall thickness of the resistance-changing layers. As a result, in response to the increased thickness, the shape, density, distribution, and arrangement of the conductive filaments generated in the first to third resistance-changing layers 120, 140, and 170 can be controlled more precisely.

[0060] exist Figure 2 In some embodiments not shown, the distance between the first electrode 110 and the second electrode 150 may be fixed, and the number of multiple resistance-changing layers disposed within that distance may be increased. Therefore, the number of conductive control layers disposed between the multiple resistance-changing layers may be increased to correspond to the increase in the number of resistance-changing layers.

[0061] As the number of resistance-varying layers increases, the thickness of each of these layers can be reduced. Therefore, the length of the conductive wires formed within each of the resistance-varying layers between the multiple conductive control layers can be shortened. With shorter conductive wire lengths, the shape, density, and arrangement of the conductive wires can be controlled more precisely.

[0062] Figures 7 to 10 This is a cross-sectional view schematically illustrating a method for manufacturing a semiconductor device according to an embodiment of the present disclosure. Figure 11A , Figure 11B , Figure 12A and Figure 12B This is a view schematically illustrating a method for forming a conductivity control layer of a semiconductor device according to an embodiment of the present disclosure.

[0063] refer to Figure 7 A substrate 101 may be provided. The substrate can be any type of substrate used in semiconductor device manufacturing processes. As an example, substrate 101 may include a semiconductor, an insulator, or a conductor.

[0064] Next, a first electrode 110 may be formed on the substrate 101. The first electrode 110 may include a conductive material. For example, the conductive material may include a doped semiconductor, a metal, a conductive metal nitride, a conductive metal carbide, a conductive metal silicide, or a conductive metal oxide. For example, the conductive material may include n-type or p-type doped silicon (Si), tungsten (W), titanium (Ti), copper (Cu), aluminum (Al), ruthenium (Ru), platinum (Pt), iridium (Ir), iridium oxide, tungsten nitride, titanium nitride, tantalum nitride, tungsten carbide, titanium carbide, tungsten silicide, titanium silicide, tantalum silicide, ruthenium oxide, or a combination of two or more thereof. The first electrode 110 may be formed using, for example, sputtering, chemical vapor deposition, or atomic layer deposition.

[0065] Next, a first resistance-changing layer 120 can be formed on the first electrode 110. The first resistance-changing layer 120 may include a resistance-changing material. The resistance-changing material may include metal oxides, such as titanium oxide, aluminum oxide, nickel oxide, copper oxide, zirconium oxide, manganese oxide, hafnium oxide, tungsten oxide, tantalum oxide, niobium oxide, and iron oxide. As another example, the resistance-changing material may include perovskite materials, such as PCMO(Pr 0.7 Ca 0.3 MnO3), LCMO(La 1- x Ca x MnO3), BSCFO(Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ ), YBCO(YBa2Cu3O) 7-x (Ba,Sr)TiO3 (doped with Cr, Nb), SrZrO3 (doped with Cr, V), (La,Sr)MnO3, Sr 1-x La x TiO3, La 1-x Sr x FeO3, La 1-x Sr x CoO3, SrFeO 2.7 Materials such as LaCoO3, RuSr2GdCu2O3, and YBa2Cu3O7. As another example, resistivity-changing materials can include selenide-based materials, such as Ge... x Se 1-x (Doped with Ag, Cu, Te), or metal sulfides such as Ag₂S, Cu₂S, CdS, ZnS, etc. The first resistivity variation layer 120 can be formed using, for example, chemical vapor deposition or atomic layer deposition.

[0066] refer to Figure 8 A metal-organic framework layer 132 can be formed on the first resistance-changing layer 120. The metal-organic framework layer 132 can be formed by sequentially stacking multiple metal-organic frameworks 132a, 132b, 132c, and 132d, such as... Figure 11A and Figure 11B As shown. Each of the plurality of metal-organic frameworks 132a, 132b, 132c and 132d may have a two-dimensional structure including a cavity V. The cavities V of the plurality of metal-organic frameworks 132a, 132b, 132c and 132d may be aligned with each other and overlap. Figure 11A This is a schematic plan view showing the metal-organic framework 132a, and Figure 11B This is a schematic perspective view showing the metal-organic framework layer 132.

[0067] Each of the plurality of metal-organic frameworks 132a, 132b, 132c, and 132d may include a metal node and an organic ligand coupled to the metal node. As an embodiment, each of the metal-organic frameworks 132a, 132b, 132c, and 132d may be as described above. Figure 4 The metal-organic framework M is described.

[0068] In an embodiment, the metal-organic framework layer 132 can be formed using a deposition method comprising a first precursor of a metal constituting a metal node and a second precursor comprising an organic ligand. The deposition method can include, for example, atomic layer deposition or chemical vapor deposition. In this case, the first metal-organic framework can be formed on the first resistivity-changing layer 120 using the deposition method, and then the deposition method can be performed on the first metal-organic framework to form a second metal-organic framework. As described above, the metal-organic framework layer 132 can be formed by the deposition method by sequentially stacking metal-organic frameworks.

[0069] In another embodiment, the process of forming the metal-organic framework layer 132 may include the following steps: preparing a first precursor comprising a metal constituting a metal node and a second precursor comprising an organic ligand; synthesizing the metal-organic framework using the first and second precursors; and coating the synthesized metal-organic framework onto the first resistivity-changing layer 120. The process of synthesizing the metal-organic framework can be performed in a liquid or gaseous state.

[0070] refer to Figure 11A and Figure 11B Each of the multiple metal-organic frameworks 132a, 132b, 132c, and 132d can have a two-dimensional structure comprising cavities V arranged at regular intervals. The width d of the cavity V can be determined by the materials constituting the metal nodes and the organic ligands. For example, the width d of the cavity V can be from 1 nm to 100 nm.

[0071] Refer again Figure 9 The conductive control layer 130 can be formed by arranging metal particles 134 within the metal-organic framework layer 132. In an embodiment, such as Figure 12A and Figure 12B As shown, the conductive control layer 130 can be formed by arranging metal particles 134 inside the overlapping cavities V of multiple metal-organic frameworks 132a, 132b, 132c and 132d. Figure 12A This is a schematic plan view showing the conductive control layer 130, and Figure 12B This is a schematic perspective view showing the conductive control layer 130.

[0072] In an embodiment, the process of forming the conductive control layer 130 may include the following process: providing a precursor comprising a metal to the metal-organic framework layer 132, and reducing the metal in the precursor to grow the metal into metal particles 134 within the internal space of the overlapping cavity V of the metal-organic framework layer 132.

[0073] In another embodiment, the process of forming the conductivity control layer 130 may include: depositing a metal layer on the first resistance variation layer 120 to fill the interior space of the overlapping cavity V of the metal-organic framework layer 132, and forming metal particles 134 by removing a portion of the metal layer deposited on the exterior of the cavity V. The process of removing the portion of the metal layer may be performed, for example, by polishing.

[0074] The metal particles 134 formed by the method described above can have any shape of aggregated metal atoms. The metal particles 134 can have various three-dimensional shapes. In an embodiment, the diameter D of the spherical metal particles 134 can be, for example, from 1 nm to 100 nm. The diameter D of the metal particles 134 can be substantially equal to or less than the width d of the cavity V. Therefore, the metal particles 134 can be disposed inside the cavity V and can be regularly arranged within the metal-organic framework layer 132. For example, the metal particles 134 can include cobalt (Co), nickel (Ni), copper (Cu), iron (Fe), platinum (Pt), gold (Au), silver (Ag), iridium (Ir), ruthenium (Ru), palladium (Pd), manganese (Mn), or combinations of two or more thereof.

[0075] refer to Figure 10A second resistance variation layer 140 can be formed on the conductive control layer 130. The material, structure, and electrical properties of the second resistance variation layer 140 can be substantially the same as those of the first resistance variation layer 120. In an embodiment, the first resistance variation layer 120 and the second resistance variation layer 140 can be formed from substantially the same material. The second resistance variation layer 140 can be formed using, for example, a chemical vapor deposition method or an atomic layer deposition method.

[0076] Next, a second electrode 150 can be formed on the second resistance variation layer 140. The material, structure, and electrical properties of the second electrode 150 can be substantially the same as those of the first electrode 110. In an embodiment, the first electrode 110 and the second electrode 150 can be formed from substantially the same material. The second electrode 150 can be formed using, for example, a chemical vapor deposition method or an atomic layer deposition method. Semiconductor devices according to embodiments of the present disclosure can be manufactured using the methods described above, and the processes can be repeated in semiconductor devices having additional resistance variation layers and conductivity control layers between the electrode layers.

[0077] Figure 13A This is a perspective view schematically illustrating a semiconductor device according to another embodiment of the present disclosure. Figure 13B yes Figure 13A A partially magnified view of a semiconductor device.

[0078] refer to Figure 13A and Figure 13B The semiconductor device 3 can be a cross-point array device. The semiconductor device 3 may include a plurality of first conductive lines 310 and a plurality of second conductive lines 320, as well as columnar structures 30 disposed at the intersections or regions of the first conductive lines 310 and second conductive lines 320. The first conductive lines 310 and second conductive lines 320 may be disposed on different planes. Figure 13B As shown, each of the columnar structures 30 may include a first resistance variation layer 312, a conductivity control layer 313, and a second resistance variation layer 314.

[0079] refer to Figure 13A In the semiconductor device 3, a plurality of first conductive lines 310 can be arranged in the y-direction, and a plurality of second conductive lines 320 can be arranged in the x-direction. A plurality of columnar structures 30 can be arranged at or in the regions where the first conductive lines 310 and the second conductive lines 320 intersect. The plurality of columnar structures 30 can extend along the z-direction. Figure 13A and Figure 13BIn the diagram, the x-direction and y-direction are shown as a Cartesian coordinate system in which the x-direction and y-direction are orthogonal to each other, but this disclosure is not limited to this, and various modifications are possible as long as the x-direction and y-direction are not parallel. In the plan view, the columnar structures 30 can be formed into multiple arrays arranged in the x-direction and y-direction. Each of the multiple columnar structures 30 can constitute a memory cell of the semiconductor device 3. The first conductive line 310 and the second conductive line 320 can be signal lines of the semiconductor device 3, and can also be conductive layers of a line type.

[0080] refer to Figure 13B The columnar structure 30 may include a first electrode layer 311 disposed on the first conductive line 310, a first resistance variation layer 312 disposed on the first electrode layer 311, a conductivity control layer 313 disposed on the first resistance variation layer 312, a second resistance variation layer 314 disposed on the conductivity control layer 313, and a second electrode layer 315 disposed on the second resistance variation layer 314.

[0081] The material and electrical properties of each of the first electrode layer 311, the first resistance variation layer 312, the conductivity control layer 313, the second resistance variation layer 314, and the second electrode layer 315 can be respectively related to... Figure 1 The materials and electrical properties of the first electrode layer 110, the first resistance change layer 120, the conductivity control layer 130, the second resistance change layer 140, and the second electrode layer 150 of the semiconductor device are basically the same.

[0082] As described above, the semiconductor device according to the embodiments of the present disclosure can be implemented as a cross-point array device comprising an array of multiple memory cells.

[0083] Figure 14A This is a perspective view schematically illustrating a semiconductor device according to another embodiment of the present disclosure. Figure 14B yes Figure 14A A partially enlarged view of a semiconductor device. (Reference) Figure 14A and Figure 14B ,and Figure 13A and Figure 13B Compared to semiconductor device 3, semiconductor device 4 may also include selection elements.

[0084] refer to Figure 14A The semiconductor device 4 may include a plurality of first conductive lines 410 and a plurality of second conductive lines 420, as well as columnar structures 40 disposed at the intersections or regions of the first conductive lines 410 and the second conductive lines 420. The first conductive lines 410 and the second conductive lines 420 may be disposed on different planes. Figure 14BAs shown, each of the columnar structures 40 may include a first electrode layer 413, a first resistance variation layer 414, a conductivity control layer 415, a second resistance variation layer 416, and a second electrode layer 417. The material, structure, and electrical properties of each of the first electrode layer 413, the first resistance variation layer 414, the conductivity control layer 415, the second resistance variation layer 416, and the second electrode layer 417 may be respectively related to... Figure 13A and Figure 13B The materials, structures and electrical properties of the first electrode layer 311, the first resistance change layer 312, the conductivity control layer 313, the second resistance change layer 314 and the second electrode layer 315 are basically the same.

[0085] refer to Figure 14B The semiconductor device 4 may further include a selection element electrode 411 and a selection element layer 412 disposed between the first conductive line 410 and the first electrode layer 413. The selection element electrode 411 may include a conductive material. The conductive material included in the selection element electrode 411 may be substantially the same as the conductive material included in the first electrode layer 413.

[0086] Selecting element layer 412 can be a switching layer that performs threshold switching operations and can reduce leakage current introduced from adjacent columnar structures when crosspoint array devices are driven.

[0087] For example, the selected element layer 412 may include silicon oxide, silicon nitride, metal oxide, metal nitride, or a combination of two or more thereof. As an example, the selected element layer 412 may include aluminum oxide, zirconium oxide, hafnium oxide, tungsten oxide, titanium oxide, nickel oxide, copper oxide, manganese oxide, tantalum oxide, niobium oxide, iron oxide, or a combination of two or more thereof.

[0088] As described above, the semiconductor device according to embodiments of the present disclosure can be implemented as a cross-point array device including an array of memory cells that additionally include a selection element layer for performing threshold switching.

[0089] Embodiments of this disclosure have been disclosed for illustrative purposes. Those skilled in the art will understand that various modifications, additions, and substitutions may be made without departing from the scope and spirit of this disclosure and the appended claims.

Claims

1. A semiconductor device, comprising: First electrode; A first resistance variation layer is disposed on the first electrode; A conductivity control layer is disposed on the first resistance change layer and includes a metal-organic framework layer and metal particles embedded in the metal-organic framework layer; A second resistance variation layer is disposed on the conductivity control layer; as well as The second electrode is disposed on the second resistance variation layer.

2. The semiconductor device according to claim 1, wherein, The metal-organic framework layer has insulating properties.

3. The semiconductor device according to claim 1, wherein, The metal-organic framework layer includes a two-dimensional metal-organic framework, which includes regularly arranged cavities.

4. The semiconductor device according to claim 3, in, The metal-organic framework layer comprises at least two metal-organic frameworks. The cavities of the at least two metal-organic frameworks are arranged to overlap each other, and The metal particles are disposed in the internal space of the overlapping cavity.

5. The semiconductor device according to claim 4, wherein, The width of the metal particles is equal to or less than the width of the cavity.

6. The semiconductor device according to claim 1, wherein, The height of the metal particles on the first resistance-changing layer is the same as or greater than the thickness of the metal-organic framework layer.

7. The semiconductor device according to claim 1, wherein, The metal particles include at least one selected from the following: cobalt (Co), nickel (Ni), copper (Cu), iron (Fe), platinum (Pt), gold (Au), silver (Ag), iridium (Ir), ruthenium (Ru), palladium (Pd), and manganese (Mn).

8. The semiconductor device according to claim 1, wherein, The metal particles are regularly arranged in the metal-organic framework layer.

9. The semiconductor device according to claim 1, wherein, The metal particles are arranged on a plane that is spaced at a predetermined distance from the first electrode or the second electrode.

10. The semiconductor device according to claim 1, wherein, The metal particles are arranged to contact the first resistance variation layer and the second resistance variation layer.

11. The semiconductor device of claim 1, further comprising a conductive wire that contacts the metal particles and extends through the first resistance variation layer and the second resistance variation layer.

12. The semiconductor device according to claim 1, further comprising a first conductive wire disposed in the first resistance variation layer and a second conductive wire disposed in the second resistance variation layer. in, The first conductive wire and the second conductive wire were not in contact with the metal particles.

13. The semiconductor device according to claim 1, wherein, The first resistance variation layer and the second resistance variation layer are formed of the same material.

14. The semiconductor device according to claim 1, further comprising: Another conductive control layer and a third resistance change layer are disposed between the second resistance change layer and the second electrode. The other conductive control layer is disposed on the second resistance variation layer; and The third resistance variation layer is disposed on the other conductive control layer.

15. A method for manufacturing a semiconductor device, the method comprising: Provide substrate; A first electrode is formed on the substrate; A first resistance variation layer is formed on the first electrode; A conductive control layer comprising an insulating metal-organic framework layer and metal particles embedded in the metal-organic framework layer is formed on the first resistance variation layer. A second resistance variation layer is formed on the conductive control layer; and A second electrode is formed on the second resistance-changing layer.

16. The method according to claim 15, wherein, Forming the conductive control layer includes: Forming a metal-organic framework with a two-dimensional structure and including cavities; Stacking multiple metal-organic frameworks to form the insulating metal-organic framework layer, wherein the cavities of the metal-organic frameworks overlap each other; and The metal particles are arranged in the internal space of the overlapping cavity.

17. The method according to claim 16, wherein, Forming the metal-organic framework includes performing an atomic layer deposition method or a chemical vapor deposition method using a first precursor and a second precursor, wherein the first precursor comprises a metal constituting a metal node and the second precursor comprises an organic ligand.

18. The method according to claim 16, wherein, Forming a metal-organic framework involves performing a synthetic operation using a first precursor and a second precursor, the first precursor comprising a metal constituting a metal node, and the second precursor comprising an organic ligand.

19. The method of claim 16, wherein, Arranging the metal particles includes: Provide the insulating metal-organic framework layer with a precursor comprising a metal; The metal of the precursor reduced in the insulating metal-organic framework layer; and The reduced metal is grown into metal particles located in the internal space of the overlapping cavity of the insulating metal-organic framework layer.

20. The method of claim 16, wherein, Arranging the metal particles includes: A metal layer is deposited to fill the internal space of the overlapping cavity of the metal-organic framework layer; and Remove a portion of the metal layer located outside the cavity.

21. A semiconductor device, comprising: A first conductive line and a second conductive line are disposed on different planes; as well as A columnar structure is disposed in the region where the first conductive line and the second conductive line intersect. The columnar structure includes a first resistance variation layer, a conductivity control layer, and a second resistance variation layer, wherein the conductivity control layer is disposed between the first resistance variation layer and the second resistance variation layer. The conductive control layer includes a metal-organic framework layer and metal particles embedded in the metal-organic framework layer.

22. The semiconductor device according to claim 21, wherein, The metal-organic framework layer has insulating properties.

23. The semiconductor device according to claim 21, wherein, The metal-organic framework layer includes a metal-organic framework with a two-dimensional structure, and the metal-organic framework includes regularly arranged cavities.

24. The semiconductor device according to claim 23, in, The metal-organic framework layer comprises at least two metal-organic frameworks. The cavities of the at least two metal-organic frameworks are arranged to overlap each other, and The metal particles are disposed in the internal space of the overlapping cavity.

25. The semiconductor device according to claim 23, wherein, The metal particles are positioned to contact the first resistance variation layer and the second resistance variation layer.

26. The semiconductor device of claim 21, further comprising: The first electrode is disposed between the first conductive line and the first resistance variation layer; as well as The second electrode is disposed between the second conductive line and the second resistance variation layer.

27. The semiconductor device of claim 21, further comprising a selection element disposed between the first conductive line and the first resistance variation layer, or between the second conductive line and the second resistance variation layer.

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