Selector, semiconductor device, and method of manufacturing selector and semiconductor device

Abstract

The invention relates to a selector, a semiconductor device and a method of manufacturing the selector and the semiconductor device. A selector includes: a carbon material including carbon and a trivalent element chemically bonded to the carbon; and a dopant material implanted into the carbon material to form trap sites of conductive carriers in the carbon material based on chemical bonds between carbon and trivalent elements. A method of manufacturing a selector includes: forming a carbon layer including carbon; carrying out chemical reaction on the trivalent elements and carbon in the carbon layer; and implanting a dopant through an ion implantation process.

Description

[0001] Priority claim and cross reference to related applications

[0002] This application claims the priority of Korean Patent Application No. 10-2023-0141542 filed on October 20, 2023 in the Korean Intellectual Property Office, which is incorporated herein by reference in its entirety. Technical Field

[0003] Embodiments of the present disclosure relate to memory circuits or devices and applications thereof in semiconductor devices. Background Art

[0004] Recent demands for miniaturization, low power consumption, high performance, and diversification of electronic devices require semiconductor devices capable of storing information in a variety of electronic devices (such as computers and portable communication devices), and researchers and the industry are studying and developing such semiconductor devices. Among semiconductor devices, some can store data by utilizing the property of switching between different resistance states according to applied voltage or current, such as resistive random access memory (RRAM), phase change random access memory (PRAM), ferroelectric random access memory (FRAM), magnetic random access memory (MRAM), and electric fuses. Summary of the invention

[0005] Embodiments of the present disclosure relate to a selector having excellent electrical and physical characteristics by using carbon as a matrix of the selector, chemically reacting the carbon with a trivalent element, and then ion-implanting a dopant, a semiconductor device including the selector, and a method of manufacturing the semiconductor device.

[0006] According to an embodiment of the present disclosure, a selector includes: a carbon material including carbon and a trivalent element chemically bonded to the carbon; and a dopant material injected into the carbon material to form trap sites for conductive carriers in the carbon material based on chemical bonds between the carbon and the trivalent element.

[0007] According to another embodiment of the present disclosure, a method of manufacturing a selector includes: forming a carbon layer including carbon; chemically reacting a trivalent element with carbon in the carbon layer to chemically bond the trivalent element and the carbon; and implanting a dopant through an ion implantation process.

[0008] According to another embodiment of the present disclosure, a semiconductor device includes a selector pattern including carbon, a trivalent element, and a dopant chemically bonded through a chemical bond between the carbon, the trivalent element, and the dopant; and a memory pattern coupled to the selector pattern.

[0009] According to another embodiment of the present disclosure, a method for manufacturing a semiconductor device includes: forming a carbon layer containing carbon; performing a chemical reaction between a trivalent element and carbon in the carbon layer; subsequently injecting a dopant into the carbon layer through an ion implantation process; forming a memory layer coupled to a selector layer; and subsequently etching the memory layer and the selector layer using a mask pattern to form a memory pattern from the memory layer and to form a selector pattern from the carbon layer having chemically bonded carbon, the trivalent element, and the dopant, thereby forming a storage cell including the memory pattern and the selector pattern. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figures 1A to 1C A method of manufacturing a selector according to an embodiment of the present disclosure is shown.

[0011] Figure 2A and Figure 2B A semiconductor device according to an embodiment of the present disclosure is shown.

[0012] Figures 3A to 3G A method of manufacturing a semiconductor device according to an embodiment of the present disclosure is shown.

[0013] FIG. 4A to FIG. 4G A method of manufacturing a semiconductor device according to another embodiment of the present disclosure is shown. DETAILED DESCRIPTION

[0014] Below, the exemplary embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. However, the present disclosure can be implemented in different forms and should not be construed as being limited to the embodiments set forth herein. On the contrary, these embodiments are provided so that the present disclosure will be thorough and complete, and the scope of the present disclosure will be fully conveyed to those skilled in the art. In the present disclosure, the same reference numerals refer to the same parts in multiple figures and embodiments of the present disclosure.

[0015] The drawings are not necessarily drawn to scale, and in some cases, the scale may be exaggerated to clearly illustrate the features of the embodiments. When a first layer is referred to as "on a second layer" or "on a substrate", it refers not only to the case where the first layer is directly formed on the second layer or substrate, but also to the case where a third layer exists between the first layer and the second layer or substrate.

[0016] Figures 1A to 1C A method of manufacturing a selector according to an embodiment of the present disclosure is shown.

[0017] exist Figures 1A to 1C In the embodiment of the present invention, a method for manufacturing a selector is shown. The following description focuses on the manufacture of the selector, and the description of the structure other than the selector located at the upper and lower parts of the selector is omitted.

[0018] refer to Figure 1A , a carbon layer CL can be formed.

[0019] The carbon layer CL can be used as a matrix to form the base of the selector. The carbon layer CL can be formed of an amorphous phase or include an amorphous phase to easily participate in a chemical reaction, and when a dopant such as arsenic (As) is ion-implanted, a new structural bond can be easily formed, and the metallic state of the dopant can be well maintained. Therefore, the ion-implanted dopant can more easily and effectively form a trap site for conductive carriers, thereby effectively realizing the threshold switching operation characteristics of the selector. As described later in this patent document, the selector has a threshold switching by presenting two different conductive states in response to an applied voltage, and is able to present (1) a conductive state, allowing current to pass through the selector, and (2) a non-conductive state, which prevents current from passing through the selector, and selectively switches between these two states, depending on whether the applied voltage is higher or lower than the threshold voltage. Since the carbon layer CL has a low density and high thermal conductivity, the selector based on the carbon layer CL can have excellent electrical and physical properties.

[0020] The carbon layer CL may be formed by depositing carbon (C) using a physical deposition method such as a sputtering method.

[0021] According to one embodiment of the present disclosure, the carbon layer CL may include carbon (C) atoms and also include at least one of nitrogen (N) atoms, oxygen (O) atoms, or hydrogen (H) atoms. For example, the carbon layer CL may include carbon (C) atoms as a main component and also include nitrogen (N) atoms, oxygen (O) atoms, or hydrogen (H) atoms as a secondary component. For example, the carbon layer CL may include carbon (C) atoms as a main component and also include any two of nitrogen (N) atoms, oxygen (O) atoms, or hydrogen (H) atoms as secondary components. For example, the carbon layer CL may include carbon (C) atoms as a main component and also include nitrogen (N) atoms, oxygen (O) atoms, and hydrogen (H) atoms as secondary components. In an embodiment, at least one of nitrogen (N) atoms, oxygen (O) atoms, or hydrogen (H) atoms may be doped into the carbon layer CL by performing a carbon (C) deposition process in an atmosphere of at least one gas of nitrogen, oxygen, or hydrogen.

[0022] The carbon layer CL may be formed to have a first thickness T1.

[0023] refer to Figure 1B , the carbon layer CL may be chemically reacted to convert or change the carbon layer CL into the chemical reaction layer 10A.

[0024] Figure 1BThe chemical reaction shown refers to causing the trivalent element to chemically react with the surface of the carbon layer CL. By using plasma doping or other treatments to include the desired chemical reaction, the trivalent element is placed in the carbon layer CL by chemically reacting with the elements contained in the carbon layer CL, without using a direct ion implantation process to implant the trivalent element into the carbon layer CL. If a direct ion implantation process is used to implant the trivalent element into the carbon layer CL, ions of the trivalent element may be implanted into the interior of the carbon layer CL by bombarding the carbon layer CL, but the implanted ions may not chemically react with the components contained in the carbon layer CL to form new structural bonds. Therefore, in various embodiments, it may be desirable to place the trivalent element in the carbon layer CL by a chemical reaction. According to an embodiment of the present disclosure, Figure 1B The chemical reaction shown can form a chemical reaction layer 10A, which includes complex chemical bonds between the components contained in the carbon layer CL and the trivalent element. As described above, the carbon layer CL may include carbon (C) atoms, and optionally may also include at least one of nitrogen (N) atoms, oxygen (O) atoms, or hydrogen (H) atoms. Therefore, the chemical reaction layer 10A may include carbon (C) as a main component, and may include complex chemical bonds formed by chemical reactions with trivalent elements. Therefore, the chemical reaction layer 10A may include chemical bonds between carbon (C) and trivalent elements formed by chemical reactions, and in addition to the chemical bonds between carbon (C) and the trivalent element, may optionally include chemical bonds between at least one of nitrogen (N), oxygen (O) or hydrogen (H) and the trivalent element.

[0025] A trivalent element may refer to an element having three valence electrons. Here, a valence electron refers to an electron among the outer electrons of an atom that can participate in a chemical bond when the outer layer is not closed. The trivalent element can control the off current characteristic by chemically reacting with an element included in the carbon layer CL to form a chemical bond and capturing some conductive carriers through holes formed by the trivalent structure to prevent excessive current.

[0026] The trivalent element capable of chemically reacting with the element included in the carbon layer CL may include at least one of boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl).

[0027] According to one embodiment of the present disclosure, when the trivalent element includes boron (B), the chemical reaction layer 10A may include a complex chemical bond formed by carbon (C), nitrogen (N), oxygen (O), hydrogen (H) or boron (B), for example, the chemical reaction layer 10A may include at least one of a BC bond, a BN bond or a BO bond.

[0028] The chemical reaction between the elements included in the carbon layer CL and the trivalent element may be a plasma chemical reaction. The plasma chemical reaction may include a plasma doping (PLAD) process. When the trivalent element chemically reacts with the carbon layer CL through the PLAD process, the trivalent element may chemically react with the elements including carbon (C) on the surface and inside the carbon layer CL to form new chemical bonds, converting or changing the carbon layer CL into a chemical reaction layer 10A having a structure and composition different from that of the carbon layer CL.

[0029] According to one embodiment of the present disclosure, the chemical reaction between the element contained in the carbon layer CL and the trivalent element can be performed at an energy of about 1 to 5 KV and a trivalent element implantation amount of about 2.5×10 15 cm -2 Up to 2.5×10 16 cm -2 When the amount of trivalent element implantation exceeds the above range, the flexibility of carbon forming the base of the selector may be reduced. As a result, it may be difficult to ensure stable physical properties of the selector.

[0030] According to one embodiment of the present disclosure, when the trivalent element includes boron (B), the energy may be about 1 to 5 KV and the trivalent element implantation amount may be about 2.5×10 15 cm -2 Up to 2.5×10 16 cm -2 The PLAD process is performed using B2H6 or BF3 plasma under the condition of . Hydrogen (H) contained in the B2H6 or BF3 plasma used in the PLAD process can form a chemical bond in the chemical reaction layer 10A.

[0031] Since the chemical reaction layer 10A includes chemical bonds formed by chemical reactions, the second thickness T2 of the chemical reaction layer 10A may be greater than the first thickness T1 of the carbon layer CL. Such an increase in thickness may have a positive effect on ensuring stable physical properties of the finally formed selector. Specifically, during the dopant ion implantation process, which is a subsequent process in the formation of the selector, the chemical reaction layer 10A is inevitably damaged by the ion implantation process. Even if the chemical reaction layer 10A is damaged, the chemical reaction layer 10A must ensure a minimum thickness in order to be used as a selector. According to this embodiment of the present disclosure, the second thickness T2 of the chemical reaction layer 10A may be greater than Figure 2B The first thickness T1 of the carbon layer CL before being converted by chemical reaction with the trivalent element is shown. Therefore, although the subsequent ion implantation process may cause damage, the stable physical characteristics of the finally formed selector can still be ensured.

[0032] In some embodiments, due to the chemical reaction between the elements contained in the carbon layer CL and the trivalent element, the surface roughness characteristics of the chemical reaction layer 10A can be improved. Since the carbon layer CL is deposited by a PVD (physical vapor deposition) method (e.g., a sputtering method), the surface roughness of the carbon layer CL may be poor. Due to the complex chemical bonds formed by the chemical reaction with the trivalent element, the surface roughness of the chemical reaction layer 10A is sufficiently reduced, so the chemical reaction layer 10A can have a flat surface.

[0033] In some embodiments, due to the newly formed complex chemical bonds, the chemical reaction layer 10A can exhibit improved density and flexibility compared to the carbon layer CL. Therefore, the physical properties of the selector can be improved.

[0034] refer to Figure 1C , the selector 10 may be formed by injecting a dopant into the chemical reaction layer 10A.

[0035] The dopant may form a trap site for conductive carriers, thereby allowing the selector 10 to perform a threshold switching operation.

[0036] The dopant may include, for example, at least one of arsenic (As), phosphorus (P), or antimony (Sb). For example, the dopant may include arsenic (As), phosphorus (P), or antimony (Sb). For example, the dopant may include any two of arsenic (As), phosphorus (P), or antimony (Sb). For example, the dopant may include arsenic (As), phosphorus (P), or antimony (Sb).

[0037] According to one embodiment of the present disclosure, the dopant may be implanted through an ion implantation process.

[0038] The selector 10 may be formed to have a third thickness T3. According to one embodiment of the present disclosure, the third thickness T3 of the selector 10 may be the same as the second thickness T2 of the chemical reaction layer 10A. According to another embodiment of the present disclosure, the third thickness T3 of the selector 10 may be less than the second thickness T2 of the chemical reaction layer 10A. This is because a portion of the upper portion of the chemical reaction layer 10A may be lost due to damage that may be generated during the ion implantation process.

[0039] According to an embodiment of the present disclosure, the selector 10 formed according to the above method may include amorphous carbon (C) as a main component and a dopant implanted by an ion implantation process, and the selector 10 may include a complex chemical bond formed by a chemical reaction between carbon (C) and a trivalent element. In addition, in addition to the chemical bond between carbon (C) and the trivalent element, the selector 10 may optionally include a chemical bond between at least one of nitrogen (N), oxygen (O) or hydrogen (H) and the trivalent element. The trivalent element may include at least one of boron (B), aluminum (Al), gallium (Ga), indium (In) or thallium (Tl), and the dopant may include at least one of arsenic (As), phosphorus (P) or antimony (Sb).

[0040] Unlike conventional doped nitride or oxide-based selectors, the selector 10 according to the embodiment of the present disclosure may include carbon (C) of an amorphous phase that can easily participate in chemical reactions as a main component, and may form complex structural bonds through chemical reactions between carbon (C) of a tetravalent element and a trivalent element, thereby forming defects or vacancies in the selector 10. Therefore, the metallic state of the dopant can be well maintained, which makes it easier and more effective to form trap sites for conductive carriers. This can further improve the electrical properties of the selector 10. In addition, since the trivalent elements that chemically react with carbon capture some conductive carriers to prevent excessive current, the off current characteristics can be controlled. In addition, the physical properties of the selector 10 can be improved due to the essential properties of carbon as a main component. In some embodiments, when the selector 10 contains at least one of nitrogen (N), oxygen (O) or hydrogen (H) in addition to carbon (C), a more complex structural bond may be formed due to the chemical reaction between the additional element and the trivalent element, thereby further increasing the degree of forming defects or vacancies in the selector 10. Therefore, by including an additional element (at least one of nitrogen (N), oxygen (O) or hydrogen (H)) in addition to carbon (C), defects or vacancies that contribute to the formation of trap sites for conductive carriers can be increased in the selector 10. Therefore, by comprehensively considering the physical and electrical properties required for the target selector 10, the degree of structural bonds formed by chemical reactions in the selector 10 can be controlled.

[0041] The selector 10 according to the embodiment of the present disclosure is formed by utilizing a chemical reaction between carbon and a trivalent element, and may have improved thickness, density, and flexibility compared to the case of using a carbon layer CL of a starting material without a chemical reaction. In an embodiment, the selector 10 may have reduced surface roughness, thereby exhibiting excellent electrical and physical properties.

[0042] The selector 10 according to an embodiment of the present disclosure may be a current regulating layer that is capable of controlling the flow of current and can reduce and / or suppress leakage current between storage elements of a semiconductor device. The selector 10 may have a threshold switching characteristic by presenting two different conductive states: a first conductive state, in which the current is blocked or hardly flows in the selector 10 when the amplitude of the voltage supplied to the selector 10 is less than a predetermined threshold voltage; and a second conductive state, in which the current flows rapidly through the selector 10 at a voltage equal to or higher than the threshold voltage. The threshold may be referred to as a threshold voltage, and the selector 10 may be turned on or off based on the threshold voltage. Since the selector 10 exhibits different conductive characteristics in response to an applied voltage relative to a threshold voltage and can therefore be controlled to be selected in one of two different conductive states by an applied voltage, the selector is used to select whether a storage cell containing the selector 10 is selected.

[0043] The selector 10 according to an embodiment of the present disclosure may be used as a selector layer of a memory cell having a structure in which a selector layer and a memory layer are stacked at the upper and lower parts of a device. Figure 2A and Figure 2B Describe in more detail.

[0044] Figure 2A and Figure 2B A semiconductor device according to an embodiment of the present disclosure is shown. Figure 2A and Figure 2B Also appears in Figures 1A to 1C The constituent elements in the embodiment will be omitted in detail.

[0045] refer to Figure 2A and Figure 2B According to an embodiment of the present disclosure, the semiconductor device may have a cross-point structure, which includes a first conductive line 110 formed on a substrate 100 and extending along a first direction (D1), a second conductive line 130 disposed on the first conductive line 110 and extending along a second direction (D2) perpendicular to the first direction (D1), and a storage unit 120 disposed at the intersection of the first conductive line 110 and the second conductive line 130.

[0046] The substrate 100 may include a semiconductor material, such as silicon. A lower structure (not shown) may be formed in the substrate 100. For example, the lower structure may include a driving circuit (not shown) electrically connected to control the first conductive line 110 and / or the second conductive line 130.

[0047] The first conductive line 110 and the second conductive line 130 may be coupled to the memory cell 120 and drive the memory cell 120 by transmitting a voltage or a current to the memory cell 120. One of the first conductive line 110 and the second conductive line 130 may be a word line, and the other may be a bit line. The first conductive line 110 and the second conductive line 130 may have a single-layer structure or a multi-layer structure including a conductive material. The conductive material may include at least one of a metal, a metal nitride, a conductive carbon material, or a combination thereof. The conductive material is not limited to the above examples, and other implementations are also possible. For example, each of the first conductive line 110 and the second conductive line 130 may include tungsten (W), titanium (Ti), tantalum (Ta), platinum (Pt), aluminum (Al), copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), lead (Pd), tungsten nitride (WN), tungsten silicide (WSi), titanium nitride (TiN), titanium silicon nitride (TiSiN), titanium aluminum nitride (TiAlN), tantalum nitride (TaN), tantalum silicon nitride (TaSiN), tantalum aluminum nitride (TaAlN), carbon (C), silicon carbide (SiC), silicon carbonitride (SiCN), or a combination thereof.

[0048] The memory cells 120 may be arranged in a matrix form in the first direction (D1) and the second direction (D2) to overlap the intersection region of the first conductive line 110 and the second conductive line 130. The size of the memory cells 120 may be equal to or smaller than the intersection region of the first conductive line 110 and the second conductive line 130, or larger than the intersection region.

[0049] The shape of the memory cell 120 may have a cylindrical shape or a square column shape, but is not limited thereto.

[0050] Spaces between the first conductive line 110 , the second conductive line 130 , and the memory cell 120 may be filled with a dielectric material (not shown).

[0051] The memory cell 120 may include a stacked structure including a lower electrode 121 , a selector pattern 122 , an intermediate electrode 123 , a memory pattern 124 , and an upper electrode 125 .

[0052] Figure 2B The selector pattern 122 shown may correspond to Figure 1C Therefore, the selector 10 shown above will be omitted. Figure 1C An embodiment of the selector pattern 122 is similar to the detailed description.

[0053] The lower electrode 121 may be disposed at the lowermost portion of the memory cell 120, electrically connected to the first conductive line 110, and serve as a transmission path for current or voltage between the first conductive line 110 and the memory cell 120. The intermediate electrode 123 may be disposed between the selector pattern 122 and the memory pattern 124, and may be used to electrically connect them to each other and physically separate them from each other. The upper electrode 125 may be disposed at the uppermost portion of the memory cell 120, and serve as a transmission path for current or voltage between the second conductive line 130 and the memory cell 120.

[0054] The lower electrode 121, the middle electrode 123 and the upper electrode 125 may have a single-layer structure or a multi-layer structure including a variety of conductive materials (such as metals, nitrides, silicide-based materials and combinations thereof). For example, the lower electrode 121, the middle electrode 123 and the upper electrode 125 may include tungsten (W), titanium (Ti), tantalum (Ta), platinum (Pt), aluminum (Al), copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), lead (Pd), chromium (Cr), tungsten nitride (WN), tungsten silicide (WSi), titanium silicide (TiSi), titanium nitride (TiN), titanium silicon nitride (TiSiN), titanium aluminum nitride (TiAlN), tantalum nitride (TaN), tantalum silicon nitride (TaSiN), tantalum aluminum nitride (TaAlN) or a combination thereof.

[0055] The lower electrode 121 , the intermediate electrode 123 , and the upper electrode 125 may be formed of or include the same material or different materials.

[0056] The lower electrode 121 , the intermediate electrode 123 , and the upper electrode 125 may have the same thickness or different thicknesses.

[0057] At least one of the lower electrode 121, the intermediate electrode 123, or the upper electrode 125 may be selectively omitted. For example, when the lower electrode 121 is omitted, the first wire 110 may replace the omitted lower electrode 121 to perform the function of the lower electrode 121. When the upper electrode 125 is omitted, the second wire 130 may replace the omitted upper electrode 125 to perform the function of the upper electrode 125.

[0058] The selector pattern 122 may be a current regulating layer configured to control current flow and may prevent current leakage from occurring between the memory cells 120 that share the first conductive line 110 or the second conductive line 130. The selector pattern 122 may have a threshold switching characteristic by presenting two different conductive states: a first conductive state in which current is blocked or hardly flows in the selector pattern 122 when the magnitude of a voltage supplied to the selector pattern 122 is less than a predetermined threshold voltage; and a second conductive state in which current rapidly flows through the selector pattern 122 at a voltage equal to or greater than the threshold voltage. The threshold may be referred to as a threshold voltage, and the selector pattern 122 may realize an on or off state based on the threshold voltage.

[0059] Unlike conventional doped nitride or oxide-based selectors, the selector pattern 122 may include amorphous carbon (C) as a main component and a dopant implanted by an ion implantation process, and may include a complex chemical bond formed by a chemical reaction between carbon (C) and a trivalent element. In addition, in addition to the chemical bond between carbon (C) and the trivalent element, the selector pattern 122 may optionally include a chemical bond between at least one of nitrogen (N), oxygen (O), or hydrogen (H) and the trivalent element. The trivalent element may include at least one of boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), and the dopant may include at least one of arsenic (As), phosphorus (P), or antimony (Sb).

[0060] The selector pattern 122 may include carbon (C) of an amorphous phase that is easily involved in chemical reactions as a main component, and may form complex structural bonds through chemical reactions between carbon (C) of a tetravalent element and a trivalent element, thereby forming defects or vacancies in the selector pattern 122. Therefore, the metallic state of the dopant can be well maintained, which enables them to more easily and effectively form trap sites for conductive carriers. This can further improve the electrical properties of the selector pattern 122. In addition, since the trivalent element that chemically reacts with carbon captures some conductive carriers to prevent excessive current, the off current characteristics can be controlled. In addition, the physical properties of the selector pattern 122 can be improved due to the essential properties of carbon as a main component. When the selector pattern 122 contains at least one of nitrogen (N), oxygen (O) or hydrogen (H) in addition to carbon (C), a more complex structural bond may be formed due to the chemical reaction between the additional element and the trivalent element, thereby further increasing the degree of formation of defects or vacancies in the selector pattern 122. Therefore, by comprehensively considering the physical and electrical characteristics required of the target selector pattern 122, the extent of structural bonds formed by chemical reactions in the selector pattern 122 can be controlled.

[0061] The selector pattern 122 according to this embodiment of the present disclosure may have improved thickness, density, and flexibility, and may have reduced surface roughness, thereby presenting excellent electrical and physical properties. In addition, when the memory pattern 124 is formed on the upper memory pattern, the flatness of the selector pattern 122 is very important for facilitating the stable crystallization of the memory pattern 124. The selector pattern 122 according to the embodiment of the present disclosure may have improved roughness characteristics due to the formation of complex structural bonds through chemical reactions. Therefore, the memory pattern 124 may be more stably crystallized.

[0062] The memory pattern 124 can store different data by switching between different resistance states according to the voltage or current applied through the upper and lower parts. The memory pattern 124 may include materials for resistive random access memory (RRAM), phase change random access memory (PRAM), ferroelectric random access memory (FRAM), magnetic random access memory (MRAM), or other memories, for example, materials with variable resistance characteristics used in RRAM, PRAM, FRAM, MRAM, or other memories. The memory pattern 124 may include transition metal oxides used in RRAM, PRAM, FRAM, MRAM, or other memories, metal oxides such as perovskite-based materials, phase change materials such as chalcogenide-based materials, ferroelectric materials, or ferromagnetic materials, etc.

[0063] For example, the memory pattern 124 may include a magnetic tunnel junction (MTJ) structure including a free layer having a changeable magnetization direction, a fixed layer having a fixed magnetization direction, and a tunnel barrier layer between the free layer and the fixed layer.

[0064] The free layer may be a layer configured to store different data by having a variable magnetization direction, which may also be referred to as a storage layer. The free layer may have one of different magnetization directions, or one of different electron spin directions, thereby switching the polarity of the free layer in the MTJ structure and changing the resistance value. According to some embodiments of the present disclosure, when a voltage or current signal (e.g., a drive current equal to or higher than a predetermined threshold) is applied to the MTJ structure, the polarity of the free layer may change or reverse. As the polarity of the free layer changes, the free layer and the fixed layer may have different magnetization directions or different electron spin directions. Therefore, the memory pattern 124 may store different data or represent different data bits. The magnetization direction of the free layer may change between a top-down direction and a bottom-up direction. This change in the magnetization direction of the free layer may be caused by a spin transfer torque generated based on an applied current or voltage.

[0065] The fixed layer may have a fixed magnetization direction, and when the magnetization direction of the free layer changes, the fixed layer does not change. The fixed layer may also be referred to as a reference layer. According to some embodiments of the present disclosure, the fixed layer may be fixed to a magnetization direction from top to bottom. According to some embodiments of the present disclosure, the fixed layer may be fixed to a magnetization direction from bottom to top.

[0066] The free layer and the fixed layer may have a single layer structure or a multilayer structure including a ferromagnetic material. For example, the free layer and the fixed layer may include an alloy including Fe, Ni or Co as a main component, such as an Fe-Pt alloy, an Fe-Pd alloy, a Co-Pd alloy, a Co-Pt alloy, a Fe-Ni-Pt alloy, a Co-Fe-Pt alloy, a Co-Ni-Pt alloy, or a Co-Fe-B alloy, or may include a stacked structure formed by a metal, such as a stacked structure such as Co / Pt, or Co / Pd, etc.

[0067] The tunnel barrier layer can realize the tunneling of electrons in both data reading operation and data writing operation. The tunnel barrier layer may include a dielectric oxide, such as MgO, CaO, SrO, TiO, VO, NbO, Al2O3, TiO2, Ta2O5, RuO2, or B2O3.

[0068] The memory pattern 124 may have a single-layer structure or may have a multi-layer structure exhibiting variable resistance characteristics by combining two or more layers. However, the embodiments of the present disclosure are not limited thereto, and the memory cell 120 may include other memory layers that can store different data in various ways instead of the memory pattern 124.

[0069] According to this embodiment of the present disclosure, the memory cell 120 may include a lower electrode 121, a selector pattern 122, an intermediate electrode 123, a memory pattern 124, and an upper electrode 125 stacked in sequence. However, the memory cell 120 may be modified in various ways as long as it has data storage characteristics. For example, at least one of the intermediate electrode 123 or the upper electrode 125 may be omitted. In addition, the positions of the selector pattern 122 and the memory pattern 124 may be interchanged. In addition, in addition to the layers 121, 122, 123, 124, and 125, the memory cell 120 may also include one or more layers (not shown) to improve the characteristics of the memory cell 120 or to improve the process. For example, it may also include at least one of the lower electrode contact or the upper electrode contact. In addition, for example, the hard mask pattern may be retained.

[0070] The memory cells 120 formed as described above may be spaced apart from each other at regular intervals, and trenches may be formed between them. The trenches between the memory cells 120 may have a height-width aspect ratio (H / W) in the following ranges, for example, about 1:1 to 40:1, or about 10:1 to 40:1, or about 10:1 to 20:1, or about 5:1 to 10:1, or about 10:1 to 15:1, or about 1:1 to 25:1, or about 1:1 to 30:1, or about 1:1 to 35:1, or 1:1 to 45:1, or about 1:1 to 40:1.

[0071] According to some embodiments of the present disclosure, the grooves may have sidewalls substantially perpendicular to the upper surface of the substrate 100. In addition, according to one embodiment of the present disclosure, adjacent grooves may be spaced apart from each other by substantially the same distance. However, according to another embodiment of the present disclosure, the spacing between adjacent grooves may vary.

[0072] Although a cross-point structure having a single memory cell 120 is described in this embodiment of the present disclosure, the cross-point structure may include two or more memory cells 120 stacked in a vertical direction.

[0073] Then, reference will be made to Figures 3A to 3G A method for manufacturing a semiconductor device according to an embodiment of the present disclosure is described. In the following description, the lower electrode layer 221A, the selector layer 222A, the intermediate electrode layer 223A, the memory layer 224A, and the upper electrode layer 225A may respectively represent material layers to be formed into the lower electrode 221, the selector pattern 222, the intermediate electrode 223, the memory pattern 224, and the upper electrode 225 through a patterning process.

[0074] refer to Figure 3A , a first conductive line 210 may be formed on a substrate 200 formed with a predetermined lower structure (not shown). The first conductive line 210 may be formed by forming a conductive layer for forming the first conductive line 210 on the substrate 200 and then etching the conductive layer using a linear mask pattern extending in a first direction (D1). The first conductive line 210 may have a single-layer structure or a multi-layer structure including a conductive material. Non-limiting examples of the conductive material may include metals, metal nitrides, conductive carbon materials, and combinations thereof.

[0075] The lower electrode layer 221A may be formed on the first conductive line 210. The lower electrode layer 221A may have a single-layer structure or a multi-layer structure including various conductive materials such as metal, nitride, silicide-based materials, and combinations thereof.

[0076] refer to Figure 3B , a carbon layer CL may be formed on the lower electrode layer 221A.

[0077] The carbon layer CL can be used as a matrix forming the base of the selector. The carbon layer CL can be formed of an amorphous phase, which can easily participate in chemical reactions, and when a dopant such as arsenic (As) is ion-implanted, a new structural bond can be easily formed and the metallic state of the dopant can be well maintained. Since the ion-implanted dopant is configured to more easily and effectively form a trap site for conductive carriers, the threshold switching operation characteristics of the selector can be effectively realized. In addition, since the carbon layer CL has a low density and high thermal conductivity, the selector based on the carbon layer CL can have excellent electrical and physical properties.

[0078] The carbon layer CL may be formed by depositing carbon (C) through a physical deposition method (eg, physical vapor deposition such as a sputtering method).

[0079] According to one embodiment of the present disclosure, the carbon layer CL may include carbon (C) atoms as a main component, and in addition to the carbon (C), the carbon layer CL may further include at least one of nitrogen (N) atoms, oxygen (O) atoms, or hydrogen (H) atoms. In this case, by performing a carbon (C) deposition process in a gas atmosphere of at least one of nitrogen, oxygen, or hydrogen, at least one of nitrogen (N) atoms, oxygen (O) atoms, or hydrogen (H) atoms may be doped onto the carbon layer CL.

[0080] The carbon layer CL may be formed to have a fourth thickness T4.

[0081] refer to Figure 3C , the carbon layer CL may be chemically reacted to convert or change the carbon layer CL into the chemical reaction layer 222B.

[0082] Figure 3C The chemical reaction shown may refer to causing the trivalent element to chemically react with the surface of the carbon layer CL. In other words, the trivalent element is not implanted into the carbon layer CL by a direct ion implantation process, but chemically reacts with the elements contained in the carbon layer CL. According to this embodiment of the present disclosure, by Figure 3C The chemical reaction shown, the chemical reaction layer 222B may include a complex chemical bond between the element contained in the carbon layer CL and the trivalent element. As described above, the carbon layer CL may include carbon (C) atoms, and it may optionally also include at least one of nitrogen (N) atoms, oxygen (O) atoms, or hydrogen (H) atoms. Therefore, the chemical reaction layer 222B may include carbon (C) as a main component, and may include a complex chemical bond formed by a chemical reaction with a trivalent element. In other words, the chemical reaction layer 222B may include a chemical bond between carbon (C) and a trivalent element formed by a chemical reaction, and in addition to the chemical bond between carbon (C) and the trivalent element, it may also optionally include a chemical bond between at least one of nitrogen (N), oxygen (O) or hydrogen (H) and the trivalent element.

[0083] The trivalent element can control the off current characteristics by chemically reacting with the elements included in the carbon layer CL to form a chemical bond and capturing some conductive carriers in holes formed due to the trivalent structure to prevent excessive current.

[0084] The trivalent element configured to chemically react with the element included in the carbon layer CL may include at least one of boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl).

[0085] In one embodiment of the present disclosure, when the trivalent element includes boron (B), the chemical reaction layer 222B may include a complex chemical bond formed by carbon (C), nitrogen (N), oxygen (O), hydrogen (H) or boron (B), for example, the chemical reaction layer 222B may include at least one of a BC bond, a BN bond or a BO bond.

[0086] The chemical reaction between the elements included in the carbon layer CL and the trivalent element may be a plasma chemical reaction, and it may include a plasma doping (PLAD) process. When the trivalent element chemically reacts with the carbon layer CL through the PLAD process, the trivalent element may chemically react with the elements including carbon (C) on the surface and inside the carbon layer CL to form new chemical bonds. As a result, it may be converted or changed into a chemical reaction layer 222B having a different structure and a different composition from the carbon layer CL.

[0087] According to one embodiment of the present disclosure, the chemical reaction between the element contained in the carbon layer CL and the trivalent element can be performed at an energy of about 1 to 5 KV and a trivalent element implantation amount of about 2.5×10 15 Up to 2.5×10 16 cm -2 When the amount of trivalent element implantation exceeds this range, the flexibility of carbon forming the base of the selector may decrease. As a result, it may be difficult to ensure stable physical properties of the selector.

[0088] According to one embodiment of the present disclosure, when the trivalent element includes boron (B), the PLAD process may be performed using B2H6 or BF3 plasma. The PLAD process may be performed at an energy of about 1 to 5 KV and a trivalent element implantation amount of about 2.5×10 15 Up to 2.5×10 16 cm -2 The hydrogen (H) contained in the B2H6 or BF3 plasma used in the PLAD process can form a chemical bond in the chemical reaction layer 222B.

[0089] Since the chemical reaction layer 222B includes chemical bonds formed by chemical reactions, the fifth thickness T5 of the chemical reaction layer 222B may be greater than the fourth thickness T4 of the carbon layer CL. In the dopant ion implantation process (which is a subsequent process when the selector pattern 222 is formed), the chemical reaction layer 222B is inevitably damaged by the ion implantation process. Therefore, even if the chemical reaction layer 222B is damaged, the chemical reaction layer 222B must ensure a minimum thickness in order to function as a selector. According to this embodiment of the present disclosure, the fifth thickness T5 of the chemical reaction layer 222B may be increased to be greater than Figure 3B The fourth thickness T4 of the carbon layer CL before the conversion based on the chemical reaction with the trivalent element is shown. Therefore, despite being damaged by the subsequent ion implantation process, stable physical characteristics of the finally formed selector pattern 222 can be ensured.

[0090] In addition, the surface roughness characteristics of the chemical reaction layer 222B can be improved by the chemical reaction between the elements contained in the carbon layer CL and the trivalent element. Since the carbon layer CL is deposited by a method such as sputtering, the surface roughness may be poor. However, since a complex chemical bond is formed by a chemical reaction with the trivalent element, the surface roughness of the chemical reaction layer 222B is sufficiently reduced, so that a flat surface can be maintained.

[0091] Furthermore, due to the complex chemical bonds, the chemical reaction layer 222B may exhibit improved density and flexibility compared to the carbon layer CL, and as a result, physical characteristics of the selector pattern 222 may be improved.

[0092] refer to Figure 3D , dopants may be injected into the chemical reaction layer 222B to form the selector layer 222A.

[0093] The dopants may form trap sites for conductive carriers, allowing the ultimately formed selector pattern 222 to perform a threshold switching operation.

[0094] The dopant may include, for example, at least one of arsenic (As), phosphorus (P), or antimony (Sb).

[0095] According to one embodiment of the present disclosure, the dopant may be implanted through an ion implantation process.

[0096] The selector layer 222A may be formed to have a sixth thickness T6. According to one embodiment of the present disclosure, the sixth thickness T6 of the selector layer 222A may be the same as the fifth thickness T5 of the chemical reaction layer 222B. According to another embodiment of the present disclosure, the sixth thickness T6 of the selector layer 222A may be less than the fifth thickness T5 of the chemical reaction layer 222B. This is because a portion of the upper portion of the chemical reaction layer 222B may be lost due to damage that may be generated during the ion implantation process.

[0097] refer to Figure 3E , an intermediate electrode layer 223A may be formed on the selector layer 222A. The intermediate electrode layer 223A may have a single-layer structure or a multi-layer structure including a variety of conductive materials, such as metals, nitrides, silicide-based materials, and combinations thereof.

[0098] A memory layer 224A may be formed on the intermediate electrode layer 223A. The memory layer 224A may be formed of a material for RRAM, PRAM, FRAM, MRAM, or other memory, for example, a material having a variable resistance characteristic for RRAM, PRAM, FRAM, MRAM, or other memory. According to one embodiment of the present disclosure, the memory layer 224A may include a transition metal oxide for RRAM, PRAM, FRAM, MRAM, or other memory, such as a metal oxide of a perovskite-based material, a phase change material such as a chalcogenide-based material, a ferroelectric material, or a ferromagnetic material, etc. According to another embodiment of the present disclosure, the memory layer 224A may have a magnetic tunnel junction (MTJ) structure including a free layer having a variable magnetization direction, a fixed layer having a fixed magnetization direction, and a tunnel barrier layer between the free layer and the fixed layer.

[0099] An upper electrode layer 225A may be formed over the memory layer 224 A. The upper electrode layer 225A may have a single-layer structure or a multi-layer structure including various conductive materials such as metal, nitride, silicide-based materials, and combinations thereof.

[0100] refer to Figure 3F By using the mask pattern as an etching mask and sequentially etching the upper electrode layer 225A, the memory layer 224A, the intermediate electrode layer 223A, the selector layer 222A and the lower electrode layer 221A, a memory cell 220 can be formed in which the lower electrode 221, the selector pattern 222, the intermediate electrode 223, the memory pattern 224 and the upper electrode 225 are stacked sequentially.

[0101] refer to Figure 3G , a second conductive line 230 may be formed over the upper electrode 225. The second conductive line 230 may be formed by depositing a conductive layer for forming the second conductive line 230 and etching the conductive layer using a linear mask pattern extending in the second direction (D2).

[0102] Through the above process, it can be formed Figure 3G The semiconductor device shown.

[0103] The semiconductor device according to the embodiment of the present disclosure may include a first conductive line 210, a memory cell 220, and a second conductive line 230 sequentially formed over a substrate 200. The memory cell 220 may include a lower electrode 221, a selector pattern 222, an intermediate electrode 223, a memory pattern 224, and an upper electrode 225 sequentially formed.

[0104] Unlike conventional doped nitride or oxide selectors, the selector pattern 222 may include amorphous carbon (C) as a main component and an ion-implanted dopant, and the selector pattern 222 may include a complex chemical bond formed by a chemical reaction between carbon (C) and a trivalent element. In addition, in addition to the chemical bond between carbon (C) and the trivalent element, the selector pattern 222 may optionally include a chemical bond between at least one of nitrogen (N), oxygen (O), or hydrogen (H) and the trivalent element. The trivalent element may include at least one of boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), and the dopant may include at least one of arsenic (As), phosphorus (P), or antimony (Sb).

[0105] The selector pattern 222 may include carbon (C) of an amorphous phase that can easily participate in a chemical reaction as a main component, and a complex structural bond may be formed by a chemical reaction between carbon (C) of a tetravalent element and a trivalent element, thereby forming defects or vacancies in the selector pattern 222. Therefore, the metal state of the dopant can be well maintained, and a trap site for conductive carriers can be formed more easily and effectively. As a result, the electrical properties of the selector pattern 222 can be further improved. In addition, the trivalent element that chemically reacts with carbon can prevent excessive current by capturing some conductive carriers. In this way, the off current characteristics can be controlled. In addition, the physical properties of the selector pattern 222 can be improved due to the essential properties of carbon as a main component. When the selector pattern 222 contains at least one of nitrogen (N), oxygen (O) or hydrogen (H) in addition to carbon (C), a more complex structural bond may be formed by a chemical reaction between the additional element and the trivalent element, thereby further increasing the degree of formation of defects or vacancies in the selector pattern 222. Therefore, the extent of structural bonds due to chemical reactions in the selector pattern 222 may be controlled by comprehensively considering the physical and electrical properties required of the target selector pattern 222 .

[0106] The selector pattern 222 according to the embodiment of the present disclosure may have improved thickness, density, and flexibility, and may have reduced surface roughness, thereby presenting excellent electrical and physical properties. In addition, when forming the upper memory pattern 224, the flatness of the selector pattern 222 is an important factor for the stable crystallization of the memory pattern 224. Since the roughness characteristics of the selector pattern 222 according to the embodiment of the present disclosure are improved by forming a complex structural bond formed by a chemical reaction, the memory pattern 224 can be more stably crystallized.

[0107] Figure 3G The substrate 200, the first conductive line 210, the memory cell 220, the second conductive line 230, the lower electrode 221, the selector pattern 222, the intermediate electrode 223, the memory pattern 224 and the upper electrode 225 shown may correspond to Figure 2B Shown are a substrate 100 , a first conductive line 110 , a memory cell 120 , a second conductive line 130 , a lower electrode 121 , a selector pattern 122 , an intermediate electrode 123 , a memory pattern 124 , and an upper electrode 125 .

[0108] According to this embodiment of the present disclosure, the selector pattern 222 is formed below the memory pattern 224. However, the relative positions of the selector pattern 222 and the memory pattern 224 may be interchanged. This will be referred to below. FIG. 4A to FIG. 4G Give a description.

[0109] FIG. 4A to FIG. 4G A method for manufacturing a semiconductor device according to another embodiment of the present disclosure is shown. The following description will focus on Figures 1A to 1C , Figure 2A and Figure 2B as well as Figures 3A to 3G In the following description, the lower electrode layer 321A, the selector layer 322A, the intermediate electrode layer 323A, the memory layer 324A, and the upper electrode layer 325A may represent material layers that form the lower electrode 321, the selector pattern 322, the intermediate electrode 323, the memory pattern 324, and the upper electrode 325 through a patterning process.

[0110] refer to Figure 4A , a first conductive line 310 may be formed on a substrate 300 formed with a predetermined lower structure (not shown). The first conductive line 310 may be formed by forming a conductive layer for forming the first conductive line 210 on the substrate 300 and then etching the conductive layer using a linear mask pattern extending in a first direction (D1).

[0111] The lower electrode layer 321A may be formed on the first conductive line 310. The lower electrode layer 321A may have a single-layer structure or a multi-layer structure including various conductive materials such as metal, nitride, silicide-based materials, and combinations thereof.

[0112] The memory layer 324A may be formed on the lower electrode layer 321 A. The memory layer 324A may be formed of a material used for RRAM, PRAM, FRAM, MRAM, or other memories, for example, a material having a variable resistance characteristic used for RRAM, PRAM, FRAM, MRAM, or other memories.

[0113] The intermediate electrode layer 323A may be formed on the memory layer 324 A. The intermediate electrode layer 323A may have a single-layer structure or a multi-layer structure including various conductive materials such as metal, nitride, silicide-based materials, and combinations thereof.

[0114] refer to Figure 4B , a carbon layer CL may be formed on the intermediate electrode layer 323A. The carbon layer CL may be formed by depositing carbon (C) through a physical deposition method (eg, physical vapor deposition or sputtering).

[0115] According to one embodiment of the present disclosure, the carbon layer CL may include carbon (C) atoms as a main component, and in addition to carbon (C), the carbon layer CL may further include at least one of nitrogen (N) atoms, oxygen (O) atoms, or hydrogen (H) atoms. In this case, at least one of nitrogen (N) atoms, oxygen (O) atoms, or hydrogen (H) atoms may be doped onto the carbon layer CL by performing a carbon (C) deposition process in a gas atmosphere of at least one of nitrogen, oxygen, or hydrogen.

[0116] The carbon layer CL may be formed to have a seventh thickness T7.

[0117] refer to Figure 4C , the carbon layer CL may be chemically reacted to convert or change the carbon layer CL into the chemical reaction layer 322B.

[0118] pass Figure 4C The chemical reaction shown, the chemical reaction layer 322B may include complex chemical bonds between the elements contained in the carbon layer CL and the trivalent element. In other words, the chemical reaction layer 322B may include chemical bonds between carbon (C) and the trivalent element formed by the chemical reaction, and in addition to the chemical bonds between carbon (C) and the trivalent element formed by the chemical reaction, the chemical reaction layer 322B may also selectively include chemical bonds between at least one of nitrogen (N), oxygen (O) or hydrogen (H) and the trivalent element.

[0119] The trivalent element capable of chemically reacting with the element contained in the carbon layer CL may include at least one of boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl).

[0120] According to one embodiment of the present disclosure, when the trivalent element includes boron (B), the chemical reaction layer 322B may include a complex chemical bond formed by carbon (C), nitrogen (N), oxygen (O), hydrogen (H) or boron (B), for example, it may include at least one of a BC bond, a BN bond or a BO bond.

[0121] The chemical reaction between the elements contained in the carbon layer CL and the trivalent element may be a plasma chemical reaction and may include a plasma doping (PLAD) process. When the trivalent element chemically reacts with the carbon layer CL through the PLAD process, the trivalent element may chemically react with the elements including carbon (C) on the surface and inside the carbon layer CL to form new chemical bonds. As a result, it may be converted or changed into a chemical reaction layer 222B having a different structure and a different composition from the carbon layer CL.

[0122] According to one embodiment of the present disclosure, the chemical reaction between the elements contained in the carbon layer CL and the trivalent element can be achieved by the PLAD process at an energy of about 1 to 5 KV and a trivalent element implantation amount of about 2.5×10 15 Up to 2.5×10 16 cm -2 When the trivalent element implantation amount exceeds the above range, the flexibility of carbon forming the base of the selector may be reduced, and thus it may be difficult to ensure stable physical properties of the selector.

[0123] According to one embodiment of the present disclosure, when the trivalent element includes boron (B), the PLAD process can be performed using B2H6 or BF3 plasma. The PLAD process can be performed at an energy of about 1 to 5 KV and a trivalent element implantation amount of about 2.5×10 15 Up to 2.5×10 16 cm -2 The hydrogen (H) contained in the B2H6 or BF3 plasma used in the PLAD process can form a chemical bond in the chemical reaction layer 222B.

[0124] Since the chemical reaction layer 322B includes chemical bonds formed by chemical reactions, the eighth thickness T8 of the chemical reaction layer 322B may be greater than the seventh thickness T7 of the carbon layer CL. Such an increase in thickness may have a positive effect on ensuring stable physical properties of the finally formed selector pattern 322.

[0125] Furthermore, a chemical reaction between the elements included in the carbon layer CL and the trivalent element may improve the surface roughness characteristics of the chemical reaction layer 322B.

[0126] Furthermore, due to the newly formed complex chemical bonds, the chemical reaction layer 322B may exhibit improved density and flexibility compared to the carbon layer CL, and thus the physical characteristics of the selector pattern 322 may be improved.

[0127] refer to Figure 4D , dopants may be implanted into the chemical reaction layer 322B to form the selector layer 322A.

[0128] The dopant may form a trap site for conductive carriers, thereby allowing the finally formed selector pattern 322 to perform a threshold switching operation.

[0129] For example, the dopant may include at least one of arsenic (As), phosphorus (P), or antimony (Sb).

[0130] According to one embodiment of the present disclosure, the dopant may be implanted through an ion implantation process.

[0131] The selector layer 322A may be formed to have a ninth thickness T9. According to one embodiment of the present disclosure, the ninth thickness T9 of the selector layer 322A may be the same as the eighth thickness T8 of the chemical reaction layer 322B. According to another embodiment of the present disclosure, the ninth thickness T9 of the selector layer 322A may be less than the eighth thickness T8 of the chemical reaction layer 322B. This is because a portion of the upper portion of the chemical reaction layer 322B may be lost due to damage that may occur during the ion implantation process.

[0132] refer to Figure 4E , an upper electrode layer 325A may be formed on the selector layer 322A. The upper electrode layer 325A may have a single-layer structure or a multi-layer structure including a variety of conductive materials, such as metals, nitrides, silicide-based materials, and combinations thereof.

[0133] refer to Figure 4F , the upper electrode layer 325A, the selector layer 322A, the intermediate electrode layer 323A, the memory layer 324A, and the lower electrode layer 321A may be sequentially etched by using the mask pattern as an etching mask. As a result, a memory cell 320 may be formed in which the lower electrode 321, the memory pattern 324, the intermediate electrode 323, the selector pattern 322, and the upper electrode 325 are sequentially stacked.

[0134] refer to Figure 4G , a second conductive line 330 may be formed over the upper electrode 325. The second conductive line 330 may be formed by depositing a conductive layer for forming the second conductive line 330 and etching the conductive layer using a linear mask pattern extending in the second direction (D2).

[0135] Through the above process, it can be formed Figure 4G The semiconductor device shown.

[0136] The semiconductor device according to the embodiment of the present disclosure may include a first conductive line 310, a memory cell 320, and a second conductive line 330 sequentially formed over a substrate 300. The memory cell 320 may include a lower electrode 321, a memory pattern 324, an intermediate electrode 323, a selector pattern 322, and an upper electrode 325 sequentially formed.

[0137] Unlike conventional doped nitride or oxide selectors, the selector pattern 322 may include amorphous carbon (C) as a main component and an ion-implanted dopant, and the selector pattern 322 may include a complex chemical bond formed by a chemical reaction between carbon (C) and a trivalent element. In addition, in addition to the chemical bond between carbon (C) and the trivalent element, the selector pattern 322 may optionally include a chemical bond between at least one of nitrogen (N), oxygen (O), or hydrogen (H) and the trivalent element. The trivalent element may include at least one of boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), and the dopant may include at least one of arsenic (As), phosphorus (P), or antimony (Sb).

[0138] The selector pattern 222 according to an embodiment of the present disclosure may have improved thickness, density, and flexibility, and may have reduced surface roughness, thereby exhibiting excellent electrical and physical characteristics.

[0139] Figure 4G The substrate 300, the first conductive line 310, the memory cell 320, the second conductive line 330, the lower electrode 321, the selector pattern 322, the intermediate electrode 323, the memory pattern 324, and the upper electrode 325 shown in FIG. 3 may correspond to Figure 3G The substrate 200, the first conductive line 210, the memory cell 220, the second conductive line 230, the lower electrode 221, the selector pattern 222, the intermediate electrode 223, the memory pattern 224 and the upper electrode 225 shown in FIG. Figure 2B Shown are a substrate 100 , a first conductive line 110 , a memory cell 120 , a second conductive line 130 , a lower electrode 121 , a selector pattern 122 , an intermediate electrode 123 , a memory pattern 124 , and an upper electrode 125 .

[0140] According to an embodiment of the present disclosure, by using carbon as a matrix of a selector, chemically reacting carbon with a trivalent element, and then ion-implanting a dopant, a selector having excellent electrical and physical properties, a semiconductor device including the selector, and a method for manufacturing the semiconductor device are provided.

[0141] While the present disclosure has been described with respect to the specific embodiments, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the present disclosure as defined in the appended claims.

Claims

1. A selector, comprising: Carbon materials, which include carbon and a trivalent element chemically bonded to the carbon; as well as A dopant material is injected into the carbon material.

2. The selector according to claim 1, wherein: The dopant material implanted into the carbon material forms a trap site for conductive carriers in the carbon material based on a chemical bond between the carbon and the trivalent element.

3. The selector according to claim 1, wherein: The trivalent element includes at least one of boron B, aluminum Al, gallium Ga, indium In or thallium Tl.

4. The selector according to claim 1, wherein: The carbon material comprises: An additional element includes at least one of nitrogen, oxygen or hydrogen, wherein the additional element forms a chemical bond with the trivalent element.

5. The selector according to claim 1, wherein: The dopant material includes at least one of arsenic As, phosphorus P or antimony Sb.

6. The selector according to claim 1, wherein: Defects or vacancies are formed by chemical bonds between the trivalent element and the carbon.

7. The selector according to claim 1, wherein: The trivalent element includes boron B, and the dopant material includes arsenic As.

8. The selector according to claim 1, wherein: The carbon in the carbon material includes carbon in an amorphous phase.

9. A method of manufacturing a selector, comprising: forming a carbon layer including carbon; causing a trivalent element to chemically react with the carbon in the carbon layer so that the trivalent element and the carbon are chemically bonded; as well as The dopants are implanted by an ion implantation process.

10. The method according to claim 9, wherein: The dopant material injected into the carbon material forms a trap site for conductive carriers in the carbon material based on a chemical bond between the carbon and the trivalent element.

11. The method according to claim 9, wherein: The forming of the carbon layer includes performing a physical vapor deposition process.

12. The method according to claim 9, wherein: The formation of the carbon layer is performed in a gas atmosphere of at least one of nitrogen, oxygen or hydrogen.

13. The method according to claim 9, wherein: Chemically reacting the trivalent element with the carbon layer includes reacting the trivalent element including at least one of boron B, aluminum Al, gallium Ga, indium In, or thallium Tl.

14. The method according to claim 9, wherein: The chemically reacting the trivalent element with the carbon layer includes performing a PLAD process, where PLAD refers to plasma doping.

15. The method according to claim 14, wherein: The PLAD process is performed at energy levels ranging from about 1 to 5 kV and about 2.5 × 10 15 Up to 2.5×10 16 cm -2 The experiment was carried out under the condition of the injection amount of trivalent elements.

16. The method according to claim 14, wherein: The PLAD process is performed using B2H6 or BF3 plasma.

17. The method according to claim 9, wherein: The thickness of the carbon layer after the chemical reaction is greater than the thickness of the carbon layer before the chemical reaction.

18. The method according to claim 9, wherein: The surface roughness of the carbon layer after the chemical reaction is smaller than the surface roughness of the carbon layer before the chemical reaction.

19. The method according to claim 9, wherein: The ion implantation process is performed using a dopant including at least one of arsenic As, phosphorus P, or antimony Sb.

20. A semiconductor device comprising: a selector pattern including carbon, a trivalent element, and a dopant, the carbon, the trivalent element, and the dopant being chemically bonded via a chemical bond between the carbon, the trivalent element, and the dopant; as well as A memory pattern is coupled to the selector pattern.

21. The semiconductor device according to claim 20, wherein: The chemically bonded carbon, the trivalent element, and the dopant form trap sites for conductive carriers in the selector pattern so that the selector pattern can assume different conductive states in response to an applied voltage relative to a threshold voltage, and The memory pattern has an electrical connection with the selector pattern based on a state of the selector pattern in one of the different conductive states.

22. The semiconductor device according to claim 20, wherein: The selector pattern controls the flow of current and prevents current leakage between memory cells, and The memory pattern stores different data by switching between different resistance states according to applied voltage or current.

23. The semiconductor device according to claim 20, further comprising at least one of the following: a first electrode disposed between the selector pattern and the substrate, or between the substrate and the memory pattern; a second electrode disposed between the selector pattern and the memory pattern; or A third electrode is located on an upper portion of the memory pattern or an upper portion of the selector pattern.

24. The semiconductor device according to claim 20, wherein: The trivalent element includes at least one of boron B, aluminum Al, gallium Ga, indium In or thallium Tl.

25. The semiconductor device according to claim 20, wherein: The selector pattern further includes a chemical bond between at least one of nitrogen, oxygen, or hydrogen and the trivalent element.

26. The semiconductor device according to claim 20, wherein: The dopant includes at least one of arsenic As, phosphorus P, or antimony Sb.

27. The semiconductor device according to claim 20, wherein: Defects or vacancies are formed by the chemical bonds in the selector pattern.

28. The semiconductor device according to claim 20, wherein: The trivalent elements include boron B, and The dopant includes arsenic As.

29. The semiconductor device according to claim 20, wherein: The carbon has an amorphous phase.

30. A method for manufacturing a semiconductor device, comprising: forming a carbon layer including carbon over a substrate; Performing a chemical reaction between a trivalent element and the carbon in the carbon layer so that the trivalent element and the carbon in the carbon layer are chemically bonded; Then, implanting a dopant into the carbon layer by an ion implantation process so that the dopant is chemically bonded to the trivalent element and the carbon; forming a memory layer coupled to the selector layer; as well as The memory layer and the selector layer are then etched using a mask pattern to form a memory pattern from the memory layer and a selector pattern from the carbon layer having chemically bonded carbon, a trivalent element, and a dopant, thereby forming a memory cell including the memory pattern and the selector pattern.

31. The method according to claim 30, further comprising at least one of the following: forming a first electrode layer between the substrate and the selector layer or between the substrate and the memory layer; forming a second electrode layer between the selector layer and the memory layer; or A third electrode layer is formed on the memory layer or on the selector layer.

32. The method of claim 30, wherein: The forming of the carbon layer includes performing a physical vapor deposition process.

33. The method of claim 30, wherein: The formation of the carbon layer is performed in a gas atmosphere of at least one of nitrogen, oxygen or hydrogen.

34. The method of claim 30, wherein: Making the trivalent element chemically react with the carbon layer includes reacting with a trivalent element including at least one of boron B, aluminum Al, gallium Ga, indium In, or thallium Tl.

35. The method of claim 30, wherein: The chemically reacting the trivalent element with the carbon layer includes performing a PLAD process, where PLAD refers to plasma doping.

36. The method of claim 35, wherein: The PLAD process has energy levels ranging from about 1 to 5 KV and about 2.5×10 15 Up to 2.5×10 16 cm -2 The experiment was carried out under the condition of the injection amount of trivalent elements.

37. The method of claim 35, wherein: The PLAD process is performed using B2H6 or BF3 plasma.

38. The method of claim 30, wherein: The thickness of the carbon layer after the chemical reaction is formed to be greater than the thickness of the carbon layer before the chemical reaction.

39. The method of claim 30, wherein: The surface roughness of the carbon layer after the chemical reaction is formed to be smaller than the surface roughness of the carbon layer before the chemical reaction.

40. The method of claim 30, wherein: The ion implantation process is performed using a dopant including at least one of arsenic As, phosphorus P, or antimony Sb.

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