Method of manufacturing In-Se-Te layer using atomic layer deposition and In-Se-Te layer manufactured by the same

Abstract

The present invention provides a method for forming an indium-selenium-tellurium layer using atomic layer deposition and an indium-selenium-tellurium layer formed using the same. A method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention comprises: a first step of supplying an indium precursor gas to a chamber to adsorb indium onto a substrate; a second step of supplying an inert purge gas to the chamber; a third step of treating the substrate with a hydrogen plasma to form the indium into an indium hydride; a fourth step of supplying an inert purge gas to the chamber; a fifth step of supplying a hydrogen providing gas, a selenium precursor gas, and a tellurium precursor gas to the chamber to react with the indium hydride to form an indium-selenium-tellurium layer on the substrate; and a sixth step of supplying an inert purge gas to the chamber.

Description

Technology Field

[0001] The technical concept of the present invention relates to a semiconductor device, and more specifically, to a method for forming an indium-selenium-tellurium layer using atomic layer deposition and an indium-selenium-tellurium layer formed using the same. Background Technology

[0002] DRAM memory offers fast read and write speeds, while NAND memory provides the advantage of large-capacity storage. Storage class memory (SCM) is steadily gaining attention as a layer to bridge the gap between DRAM and NAND memory, which possess such different characteristics. Phase change memory is a candidate for this type of SCM, but it faces limitations due to thermal interference associated with device miniaturization and manufacturing process complexity. Recently, to overcome these limitations, a selector-only memory capable of memory operation in a simple structure containing only ovonic threshold switching materials, excluding Ge-Sb-Te (GST) materials, has been proposed. Since selector-only memory exhibits a large memory window and threshold voltage shift characteristics dependent on voltage polarity, it holds potential as a next-generation SCM device.

[0003] Selector-only memory devices reported to date are based on complex compositions of quaternary or higher, such as Si-Te-As-Ge, which makes it difficult to fabricate devices with various three-dimensional structures. Additionally, they have the disadvantage of containing toxic arsenic (As) materials. Therefore, there is a need to develop an ovonic threshold switching material layer composed of a simple composition. The problem to be solved

[0004] The technical problem that the technical concept of the present invention aims to solve is to provide a method for forming an indium-selenium-tellurium layer using atomic layer deposition and an indium-selenium-tellurium layer formed using the same.

[0005] However, these tasks are exemplary, and the technical concept of the present invention is not limited thereto. means of solving the problem

[0006] According to one aspect of the present invention, a method for forming an indium-selenium-tellurium layer using atomic layer deposition and an indium-selenium-tellurium layer formed using the same are provided.

[0007] According to one embodiment of the present invention, a method for forming an indium-selenium-tellurium layer using the atomic layer deposition method may include: a first step of supplying an indium precursor gas to a chamber to adsorb indium onto a substrate; a second step of supplying an inert purge gas to the chamber; a third step of treating the substrate with hydrogen plasma to form the indium into an indium hydride; a fourth step of supplying an inert purge gas to the chamber; a fifth step of supplying a hydrogen providing gas, a selenium precursor gas, and a tellurium precursor gas to the chamber to react with the indium hydride to form an indium-selenium-tellurium layer on the substrate; and a sixth step of supplying an inert purge gas to the chamber.

[0008] According to one embodiment of the present invention, in the third step, the indium oxide formed from the indium precursor gas can be formed into an indium hydride by the hydrogen plasma treatment.

[0009] According to one embodiment of the present invention, in the fifth step, the selenium precursor gas may react with the hydrogen providing gas to form a selenium hydride, and the tellurium precursor gas may react with the hydrogen providing gas to form a tellurium hydride.

[0010] According to one embodiment of the present invention, in the fifth step, the indium hydride formed from the indium precursor gas can react with the selenium hydride and the tellurium hydride to form the indium-selenium-tellurium layer.

[0011] According to one embodiment of the present invention, in the fifth step, the indium provided from the indium precursor gas and adsorbed on the substrate can react with the selenium hydride and the tellurium hydride to form the indium-selenium-tellurium layer.

[0012] According to one embodiment of the present invention, the indium-selenium-tellurium layer is, In x (Se, Te) 1-x It can have a chemical formula of (0.1 ≤ x ≤ 0.9).

[0013] According to one embodiment of the present invention, in the indium-selenium-tellurium layer, the atomic ratio of selenium (Se) to tellurium (Te) may have a range of 1:10 to 10:1.

[0014] According to one embodiment of the present invention, in the fifth step, while supplying the hydrogen providing gas, the selenium precursor gas and the tellurium precursor gas may be supplied.

[0015] According to one embodiment of the present invention, in the fifth step, the selenium precursor gas and the tellurium precursor gas can be supplied simultaneously.

[0016] According to one embodiment of the present invention, in the fifth step, after supplying the selenium precursor gas, the tellurium precursor gas can be supplied.

[0017] According to one embodiment of the present invention, in the fifth step, after supplying the tellurium precursor gas, the selenium precursor gas can be supplied.

[0018] According to one embodiment of the present invention, steps 1 through 6 may be performed repeatedly.

[0019] According to one embodiment of the present invention, the indium precursor gas may include at least one of [3-(dimethylamino)propyl]dimethyl indium (DADI), trimethylindium (TMI), triethylindium (TEI), tris(dimethylamido)indium (TDAI), indium guanidinate, indium amidinate, indium trichloride, indium (III) acetylacetonate, indium (III) isopropoxide, and indium (III) formamidinate.

[0020] According to one embodiment of the present invention, the selenium precursor gas may include at least one of bis(trimethylsilyl) selenide (BTMSSe), bis(tert-butyldimethylsilyl) selenide, hydrogen selenide, diethyl selenide, dimethyl selenide, and selenourea.

[0021] According to one embodiment of the present invention, the tellurium precursor gas may include at least one of bis(trimethylsilyl) telluride (BTMSTe), bis(tert-butyldimethylsilyl) telluride, hydrogen telluride, diethyl telluride, dimethyl telluride, and tellurourea.

[0022] According to one embodiment of the present invention, the hydrogen providing gas may include at least one of methanol, ammonia, ethanol, 1-propanol, benzyl alcohol, phenol, methylamine, ethylamine, dimethylamine, triethylamine, pyridine, and benzenethiol.

[0023] According to one embodiment of the present invention, a method for forming an indium-selenium-tellurium layer using the atomic layer deposition method may include the steps of: supplying an indium precursor gas to a chamber to adsorb indium onto a substrate; treating the substrate with hydrogen plasma; supplying a selenium precursor gas to the chamber along with a hydrogen providing gas to react with the indium to form an indium-selenium compound; supplying an indium precursor gas to the chamber to adsorb indium onto the substrate; treating the substrate with hydrogen plasma; and supplying a tellurium precursor gas to the chamber along with a hydrogen providing gas to react with the indium to form an indium-tellurium compound, and thereby forming an indium-selenium-tellurium layer by a combination of the indium-selenium compound and the indium-tellurium compound.

[0024] According to one embodiment of the present invention, a method for forming an indium-selenium-tellurium layer using the atomic layer deposition method may include the steps of: supplying an indium precursor gas to a chamber to adsorb indium onto a substrate; treating the substrate with hydrogen plasma; supplying a tellurium precursor gas to the chamber along with a hydrogen providing gas to react with the indium to form an indium-tellurium compound; supplying an indium precursor gas to the chamber to adsorb indium onto a substrate; treating the substrate with hydrogen plasma; and supplying a selenium precursor gas to the chamber along with a hydrogen providing gas to react with the indium to form an indium-selenium compound, and thereby forming an indium-selenium-tellurium layer by combining the indium-tellurium compound and the indium-selenium compound.

[0025] According to one embodiment of the present invention, the indium-selenium-tellurium layer is formed by a method for forming an indium-selenium-tellurium layer using the atomic layer deposition method described above, and In x (Se, Te) 1-x It can have a chemical formula of (0.1 ≤ x ≤ 0.9). Effects of the invention

[0026] According to the technical concept of the present invention, the indium-selenium-tellurium layer formed by the method of forming an indium-selenium-tellurium layer is an ovonic threshold switching composition for selector-only memory and can be applied as a selector for a next-generation memory device for storage-class memory. In addition, the indium-selenium-tellurium layer can be applied to a neuromorphic device.

[0027] With the characteristics of a selector-only memory device that has advantages over phase-change memory in terms of low power consumption, high-speed operation, and mass production, it can be utilized as an edge device that enables real-time learning and inference in various IoT terminals of smart cities, as well as in homes or on portable mobile devices.

[0028] The effects of the present invention described above are illustrative and the scope of the present invention is not limited by these effects. Brief explanation of the drawing

[0029] FIG. 1 is a flowchart illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention. FIGS. 2 to 4 are timing diagrams illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention. FIG. 5 is a flowchart illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention. FIG. 6 is a timing diagram illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention. FIG. 7 is a flowchart illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention. FIG. 8 is a timing diagram illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention. Specific details for implementing the invention

[0030] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings. The embodiments of the present invention are provided to more completely explain the technical concept of the present invention to those skilled in the art, and the following embodiments may be modified in various different forms, and the scope of the technical concept of the present invention is not limited to the following embodiments. Rather, these embodiments are provided to make the present disclosure more faithful and complete and to fully convey the technical concept of the present invention to those skilled in the art. In this specification, the same reference numerals denote the same elements throughout. Furthermore, various elements and areas in the drawings are depicted schematically. Accordingly, the technical concept of the present invention is not limited by the relative sizes or spacing depicted in the attached drawings.

[0031] The materials, process conditions, etc. described below are exemplary, and the technical concept of the present invention is not limited thereto.

[0032] According to the technical concept of the present invention, by securing a simple metal chalcogenide composition, a selector only memory (SOM) device with a three-dimensional structure can be easily manufactured, and in particular, when manufacturing a memory device having a three-dimensional high-density vertical structure, the composition of a simple material can simplify the semiconductor process.

[0033] Research on selector-only memory devices with simple compositions, such as binary or ternary systems, is in the early stages, although they have advantages in terms of performance and cost compared to phase change memory devices equipped with conventional ovonic threshold switching.

[0034] Generally known chalcogenide-based ovonic threshold switch (OTS) materials are broadly classified into two categories. First, there are materials that exhibit threshold switching (TS) characteristics. Examples include Si-Te-As-Ge, In-Te, and Al20As25Te55, in which atomic movement is suppressed in response to an externally applied voltage. Second, there are materials that exhibit memory switching (MS) characteristics. Examples include Ge-Sb-Te, In-Se, and Al20As5Te75, in which atomic movement (i.e., a change in atomic structure between crystalline and amorphous states) is activated in response to an externally applied voltage.

[0035] The indium-selenium-tellurium layer according to the technical concept of the present invention is designed to enable atomic movement in a threshold switching material composition.

[0036] Table 1 shows the standard enthalpy of formation of materials related to the manufacture of an indium-selenium-tellurium layer according to the technical concept of the present invention.

[0037] substance Standard enthalpy of formation (ΔH f o ) (kJ / mol) In2O3 -925.2 In x yourself 1-x -116.1 ~ -71.2 kJ And x Yes 1-x -326.4 ~ -118.0 InH -31.5

[0038] Referring to Table 1, the smaller the standard enthalpy of formation, the easier the formation; therefore, in the case of indium, indium oxide (In2O3) can be formed most easily. On the other hand, indium hydride (InH) is difficult to form because its standard enthalpy of formation is relatively high. Therefore, oxygen is removed from the reaction environment and hydrogen is supplied to induce the formation of the intermediate product InH instead of indium oxide (In2O3), and then a tellurium (Te) precursor or a selenium (Se) precursor is injected to form In x Te 1-x or In x Se 1-xIt can form. When injecting a tellurium precursor or a selenium precursor, a hydrogen donor such as methanol or ammonia can be simultaneously reacted as a co-reactant to provide an intermediate product of H2Te or H2Se.

[0039] Transition state energies can be calculated based on density functional theory simulations. In the reaction between the indium precursor DADI and the tellurium precursor BTMSTe, the transition state energy is 1.75 eV, whereas in the reaction between the DADI and the tellurium hydride TeH2, the transition state energy is 0.55 eV. Additionally, in the reaction between the DADI and the selenium precursor BTMSSe, the transition state energy is 1.80 eV, whereas in the reaction between the DADI and the selenium hydride SeH2, it is 0.75 eV. Therefore, it can be seen that the reaction between the indium precursor and the tellurium hydride, which have relatively low transition state energies, is easier than that between the indium precursor and the tellurium precursor. Additionally, it can be seen that the reaction between the indium precursor and the selenium hydride, which have relatively low transition state energies, is easier than that between the indium precursor and the selenium precursor.

[0040] FIG. 1 is a flowchart illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention.

[0041] Referring to FIG. 1, a method (S100) for forming an indium-selenium-tellurium layer using atomic layer deposition comprises: a first step (S110) of supplying an indium precursor gas to a chamber to adsorb indium onto a substrate; a second step (S120) of supplying an inert purge gas to the chamber; a third step (S130) of treating the substrate with hydrogen plasma to form the indium into an indium hydride; a fourth step (S140) of supplying an inert purge gas to the chamber; a fifth step (S150) of supplying a hydrogen providing gas, a selenium precursor gas, and a tellurium precursor gas to the chamber to react with the indium hydride to form an indium-selenium-tellurium layer on the substrate; and a sixth step (S160) of supplying an inert purge gas to the chamber.

[0042] In order to form the indium-selenium-tellurium layer to a desired thickness, the first step (S110) to the sixth step (S160) may be repeated. For example, as shown in FIG. 2 below, when the process of the first cycle is completed, the process of the second cycle in the same manner may be performed, and the process of subsequent cycles may be further performed.

[0043] The first step (S110) above can be performed by supplying an indium precursor gas to a chamber to adsorb indium onto a substrate. At this time, the adsorbed indium may include pure indium, indium compounds, indium oxides, etc.

[0044] The first step (S110) above can be performed by atomic layer deposition at a temperature above room temperature, for example, at a temperature in the range of 0°C to 400°C, for example, at a temperature in the range of 200°C to 350°C, for example, at 250°C. In this way, by performing the atomic layer deposition at a relatively low temperature, thermal damage to other devices or structures formed on the substrate can be prevented or minimized.

[0045] The chamber may provide a space in which the substrate is loaded and atomic layer deposition is performed on the substrate. Additionally, various devices for atomic layer deposition may be connected to the chamber.

[0046] The above substrate may be various substrates used in semiconductor devices, for example, may include a semiconductor wafer or a semiconductor epitaxial layer, may include silicon, germanium, silicon-germanium, etc. as a semiconductor material, and may include silicon oxide (SiO2), aluminum oxide (Al2O3), titanium oxide (TiO2), zirconium oxide (ZrO2), hafnium oxide (HfO2), lanthanum oxide (La2O3), etc. as an oxide. However, this is exemplary and the technical concept of the present invention is not limited thereto.

[0047] The above indium precursor gas may be supplied into the chamber by a carrier gas such as nitrogen gas. The flow rate of the above indium precursor gas may vary. In addition, the following other precursor gases may also be supplied into the chamber by a carrier gas. The flow rates of the above other precursor gases may vary.

[0048] The above indium precursor gas can be decomposed within the chamber, and accordingly, pure indium, an indium compound, or an indium oxide can be adsorbed onto the substrate to form an indium-containing layer.

[0049] The above indium precursor gas may be a gas that provides indium. The above indium precursor gas may include, for example, at least one of [3-(dimethylamino)propyl]dimethyl indium (DADI), trimethylindium (TMI), triethylindium (TEI), tris(dimethylamido)indium (TDAI), indium guanidinate, indium amidinate, indium trichloride, indium (III) acetylacetonate, indium (III) isopropoxide, and indium (III) formamidinate.

[0050] The second step (S120) above may be performed by supplying an inert purge gas to the chamber. Accordingly, by-products or unreacted materials of the indium precursor gas, etc., can be discharged to the outside of the chamber as they are purged by the inert purge gas. The inert purge gas is at room temperature (approx. 25°C). o It can be supplied via C), and the flow rate of the inert purge gas can be varied. The inert purge gas may include nitrogen gas or argon gas.

[0051] The third step (S130) above may be performed by treating the substrate with hydrogen plasma to form indium hydride from the indium. The hydrogen plasma treatment may treat the substrate surface by activating hydrogen gas into a plasma state to form high-energy hydrogen ions or hydrogen radicals, etc. Through the hydrogen plasma treatment, the indium oxide formed from the indium precursor gas may be formed into indium hydride (In-H). The third step (S130) may be performed, for example, at a temperature in the range of 0°C to 400°C, or for example, at a temperature in the range of 20°C to 300°C.

[0052] Indium has a strong bonding affinity with oxygen, making it easy to form indium oxide; however, indium or indium oxide can be formed into indium hydride through hydrogen plasma treatment. Since the indium-selenium-tellurium bond is more stable than the bond of indium hydride, indium-selenium-tellurium can be formed in a subsequent process. In other words, by forming indium hydride through hydrogen plasma treatment, the formation of indium oxide is suppressed, and the desired indium-selenium-tellurium layer can be easily formed. This is as described above.

[0053] The above fourth step (S140) may be performed by supplying an inert purge gas to the chamber. Accordingly, by-products of the indium precursor gas, hydrogen ions or hydrogen radicals as by-products of the hydrogen plasma treatment, or unreacted materials, etc., may be discharged to the outside of the chamber as they are purged by the inert purge gas. The inert purge gas is at room temperature (approx. 25°C). o It can be supplied via C), and the flow rate of the inert purge gas can be varied. The inert purge gas may include nitrogen gas or argon gas.

[0054] The above fifth step (S150) can be performed by supplying a hydrogen providing gas, a selenium precursor gas, and a tellurium precursor gas to the chamber and reacting them with the indium hydride to form an indium-selenium-tellurium layer on the substrate.

[0055] In the above fifth step (S150), atomic layer deposition can be performed at a temperature above room temperature, for example, at a temperature in the range of 0°C to 400°C, for example, at a temperature in the range of 200°C to 350°C, for example, at 250°C. In this way, by performing the atomic layer deposition at a relatively low temperature, thermal damage to other devices or structures formed on the substrate can be prevented or minimized.

[0056] In the above fifth step (S150), the selenium precursor gas may react with the hydrogen providing gas to form selenium hydride. Additionally, the tellurium precursor gas may react with the hydrogen providing gas to form tellurium hydride.

[0057] The indium hydride formed from the indium precursor gas can react with the selenium hydride and the tellurium hydride to form the indium-selenium-tellurium layer. Additionally, the indium provided from the indium precursor gas and adsorbed on the substrate can react with the selenium hydride and the tellurium hydride to form the indium-selenium-tellurium layer.

[0058] Indium requires high energy to react with other substances, and therefore, it is necessary to lower the reaction energy to chemically bond with selenium and tellurium. Therefore, selenium and tellurium can be reacted with a hydrogen-providing gas, which is a co-reactant, to form selenium hydride and tellurium hydride, respectively, which are intermediate products that are easy to chemically bond with indium.

[0059] In addition, since the indium-selenium-tellurium bond is more stable than that of indium hydride, the formed indium hydride can be converted into indium-selenium-tellurium. Therefore, it is possible to prevent the oxidation of indium and form a stable indium-selenium-tellurium layer.

[0060] The selenium precursor gas may be a gas that provides selenium. The selenium precursor gas may include, for example, at least one of bis(trimethylsilyl) selenide (BTMSSe), bis(tert-butyldimethylsilyl) selenide, hydrogen selenide, diethyl selenide, dimethyl selenide, and selenourea.

[0061] The above tellurium precursor gas may be a gas that provides tellurium. The above tellurium precursor gas may include, for example, at least one of bis(trimethylsilyl) telluride (BTMSTe), bis(tert-butyldimethylsilyl) telluride, hydrogen telluride, diethyl telluride, dimethyl telluride, and tellurourea.

[0062] The hydrogen providing gas may be a gas that provides hydrogen and may be referred to as a co-reactant. The hydrogen providing gas may include, for example, at least one of methanol, ammonia, ethanol, 1-propanol, benzyl alcohol, phenol, methylamine, ethylamine, dimethylamine, triethylamine, pyridine, and benzenethiol.

[0063] The above sixth step (S160) may be performed by supplying an inert purge gas to the chamber. Accordingly, by-products of the hydrogen supply gas, by-products of the selenium precursor gas, and by-products of the tellurium precursor gas, or unreacted materials, etc., may be discharged to the outside of the chamber as they are purged by the inert purge gas. The inert purge gas is at room temperature (approx. 25°C o It can be supplied via C), and the flow rate of the inert purge gas can be varied. The inert purge gas may include nitrogen gas or argon gas.

[0064] The indium-selenium-tellurium layer formed accordingly is In x (Se, Te) 1-x It may have a chemical formula of (0.1 ≤ x ≤ 0.9). For example, the indium-selenium-tellurium layer having chemical formulas such as InSeTe, In2Se3Te3, InSe2Te2 is also included in the technical scope of the present invention.

[0065] In the above indium-selenium-tellurium layer, the atomic ratio of selenium (Se) and tellurium (Te) may, for example, range from 1:10 to 10:1, range from 1:3 to 3:1, and for example, 1:1.

[0066] The supply method, supply temperature, and supply time of the above gases for atomic layer deposition can be varied. Exemplary process conditions are described below.

[0067] The indium precursor gas, the selenium precursor gas, and the tellurium precursor gas can be supplied in a bubbler type, and the hydrogen supply gas can be supplied in a singular type.

[0068] The above indium precursor gas is, for example, 0 o C to 100 o Temperatures in the C range, for example, about 70 o It can be stored in a storage container at a temperature of C. The selenium precursor gas and the tellurium precursor gas are, for example, 0 o C to 100 o Temperatures in the C range, for example, about 35 o It can be stored in a storage container at a temperature of C. The hydrogen supply gas is, for example, 0 o C to 100 o Temperatures in the C range, for example, room temperature (about 25°C) o C) can be stored in a storage container. Subsequently, each gas, for example, 50 o C to 150 o Temperatures in the C range, for example, 100 o It can be supplied to the chamber through piping at a temperature of C. The chamber can be maintained at a temperature in the range of, for example, 50°C to 400°C.

[0069] FIGS. 2 to 4 are timing diagrams illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention.

[0070] Referring to FIGS. 2 to 4, the timing for supplying an indium precursor, hydrogen plasma treatment, supplying a selenium precursor, supplying a tellurium precursor, supplying a hydrogen providing gas, and purging treatment is shown. The time for each process to be performed can vary, for example, the supply of precursors such as indium, selenium, and tellurium can be configured for 1 to 5 seconds, hydrogen plasma treatment for 1 to 5 seconds, hydrogen providing gas supply for 1 to 10 seconds, and purging treatment for 1 to 60 seconds. For example, the supply of precursors such as indium, selenium, and tellurium can be configured for 2 seconds, hydrogen plasma treatment for 2 seconds, hydrogen providing gas supply for 4 seconds, and purging treatment for 15 seconds. However, this is exemplary, and the technical concept of the present invention is not limited thereto.

[0071] The gas supply performed in step 5 (S150) of Fig. 1 will be described.

[0072] Referring to FIG. 2, while supplying the hydrogen providing gas, the selenium precursor gas and the tellurium precursor gas can be supplied. Additionally, the selenium precursor gas and the tellurium precursor gas can be supplied simultaneously.

[0073] Referring to FIG. 3, after supplying the selenium precursor gas, the tellurium precursor gas can be supplied. At this time, the supply of the hydrogen providing gas is continued.

[0074] Referring to FIG. 4, after supplying the tellurium precursor gas, the selenium precursor gas can be supplied. At this time, the supply of the hydrogen providing gas is continued.

[0075] FIG. 5 is a flowchart illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention.

[0076] Referring to FIG. 5, a method for forming an indium-selenium-tellurium layer using atomic layer deposition (S200) may include the steps of: supplying an indium precursor gas to a chamber to adsorb indium onto a substrate (S210); treating the substrate with hydrogen plasma (S220); supplying a selenium precursor gas to the chamber along with a hydrogen providing gas to react with the indium to form an indium-selenium compound (S230); supplying an indium precursor gas to the chamber to adsorb indium onto the substrate (S240); treating the substrate with hydrogen plasma (S250); and supplying a tellurium precursor gas to the chamber along with a hydrogen providing gas to react with the indium to form an indium-tellurium compound, thereby forming an indium-selenium-tellurium layer by a combination of the indium-selenium compound and the indium-tellurium compound (S260).

[0077] Between each step (S210 to S260), a step of purging by supplying an inert purge gas as described above with reference to FIG. 1 may be further included.

[0078] FIG. 6 is a timing diagram illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention.

[0079] Referring to FIG. 6, a timing diagram for the formation method of FIG. 5 is shown. After the selenium precursor gas is supplied, the tellurium precursor gas is supplied. During the supply of the selenium precursor gas and the supply of the tellurium precursor gas, the supply of the hydrogen providing gas is continuously performed.

[0080] FIG. 7 is a flowchart illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention.

[0081] Referring to FIG. 7, a method for forming an indium-selenium-tellurium layer using atomic layer deposition (S300) may include the steps of: supplying an indium precursor gas to a chamber to adsorb indium onto a substrate (S310); treating the substrate with hydrogen plasma (S320); supplying a tellurium precursor gas to the chamber along with a hydrogen providing gas to react with the indium to form an indium-tellurium compound (S330); supplying an indium precursor gas to the chamber to adsorb indium onto a substrate (S340); treating the substrate with hydrogen plasma (S350); and supplying a selenium precursor gas to the chamber along with a hydrogen providing gas to react with the indium to form an indium-selenium compound, thereby forming an indium-selenium-tellurium layer by a combination of the indium-tellurium compound and the indium-selenium compound (S360).

[0082] Between each step (S310~S360), a step of purging by supplying an inert purge gas as described above with reference to FIG. 1 may be further included.

[0083] FIG. 8 is a timing diagram illustrating a method for forming an indium-selenium-tellurium layer using atomic layer deposition according to an embodiment of the present invention.

[0084] Referring to FIG. 8, a timing diagram for the formation method of FIG. 7 is shown. After the tellurium precursor gas is supplied, the selenium precursor gas is supplied. In the timing diagram, the configuration is the same as FIG. 6 except that the timing of supplying the selenium precursor gas and the timing of supplying the tellurium precursor gas are alternate.

[0085] Formed by the method for forming an indium-selenium-tellurium layer using the atomic layer deposition method described above, and In x (Se, Te) 1-x An indium-selenium-tellurium layer having the chemical formula (0.1 ≤ x ≤ 0.9) can be formed.

[0086] As described above, In x (Se, Te) 1-x (0.1 ≤ x ≤ 0.9) The material may simultaneously possess memory switching (MS) and threshold switching (TS) characteristics or have intermediate characteristics. The memory switching is based on crystallization / amorphization caused by the migration of atoms within the material. The threshold switching is based on a switching operation model primarily derived from the delocalization / localization of charged defects or traps within the material. The selector-only memory device not only performs switching operations at high speed but can also have switching voltages of different magnitudes depending on the polarity of the external voltage application.

[0087] It will be obvious to those skilled in the art that the technical concept of the present invention described above is not limited to the aforementioned embodiments and attached drawings, and that various substitutions, modifications, and changes are possible within the scope of the technical concept of the present invention. Accordingly, the scope of rights of the present invention should be determined by the claims set forth below.

Claims

Claim 1 A first step of supplying an indium precursor gas to a chamber to adsorb indium onto a substrate; a second step of supplying an inert purge gas to the chamber; a third step of treating the substrate with hydrogen plasma to form the indium into an indium hydride; a fourth step of supplying an inert purge gas to the chamber; and a fifth step of supplying a hydrogen providing gas, a selenium precursor gas, and a tellurium precursor gas to the chamber to react with the indium hydride, thereby forming an indium-selenium-tellurium layer on the substrate. A method for forming an indium-selenium-tellurium layer using atomic layer deposition, comprising a sixth step of supplying an inert purge gas to the chamber, wherein in the third step, the indium oxide formed from the indium precursor gas is formed into an indium hydride by the hydrogen plasma treatment, and in the fifth step, the selenium precursor gas reacts with the hydrogen providing gas to form a selenium hydride, the tellurium precursor gas reacts with the hydrogen providing gas to form a tellurium hydride, and the indium hydride reacts with the selenium hydride and the tellurium hydride to form the indium-selenium-tellurium layer. Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 delete Claim 6 In claim 1, the indium-selenium-tellurium layer is, In x (Se, Te) 1-x A method for forming an indium-selenium-tellurium layer using atomic layer deposition having the chemical formula (0.1 ≤ x ≤ 0.9). Claim 7 A method for forming an indium-selenium-tellurium layer using atomic layer deposition, wherein, in the indium-selenium-tellurium layer, the atomic ratio of selenium (Se) to tellurium (Te) is in the range of 1:10 to 10:

1. Claim 8 A method for forming an indium-selenium-tellurium layer using atomic layer deposition, wherein, in the fifth step, the selenium precursor gas and the tellurium precursor gas are supplied while the hydrogen providing gas is supplied. Claim 9 A method for forming an indium-selenium-tellurium layer using atomic layer deposition, wherein, in the fifth step, the selenium precursor gas and the tellurium precursor gas are supplied simultaneously. Claim 10 A method for forming an indium-selenium-tellurium layer using atomic layer deposition, wherein, in the fifth step, after supplying the selenium precursor gas, the tellurium precursor gas is supplied. Claim 11 A method for forming an indium-selenium-tellurium layer using atomic layer deposition, wherein, in the fifth step, after supplying the tellurium precursor gas, the selenium precursor gas is supplied. Claim 12 A method for forming an indium-selenium-tellurium layer using atomic layer deposition, wherein, in claim 1, steps 1 through 6 are performed repeatedly. Claim 13 A method for forming an indium-selenium-tellurium layer using atomic layer deposition, wherein the indium precursor gas comprises at least one of [3-(dimethylamino)propyl]dimethyl indium (DADI), trimethylindium (TMI), triethylindium (TEI), tris(dimethylamido)indium (TDAI), indium guanidinate, indium amidinate, indium trichloride, indium (III) acetylacetonate, indium (III) isopropoxide, and indium (III) formamidinate. Claim 14 A method for forming an indium-selenium-tellurium layer using atomic layer deposition, wherein the selenium precursor gas comprises at least one of bis(trimethylsilyl) selenide (BTMSSe), bis(tert-butyldimethylsilyl) selenide, hydrogen selenide, diethyl selenide, dimethyl selenide, and selenourea. Claim 15 A method for forming an indium-selenium-tellurium layer using atomic layer deposition, wherein the tellurium precursor gas comprises at least one of bis(trimethylsilyl) telluride (BTMSTe), bis(tert-butyldimethylsilyl) telluride, hydrogen telluride, diethyl telluride, dimethyl telluride, and tellurourea. Claim 16 A method for forming an indium-selenium-tellurium layer using atomic layer deposition, wherein the hydrogen providing gas comprises at least one of methanol, ammonia, ethanol, 1-propanol, benzyl alcohol, phenol, methylamine, ethylamine, dimethylamine, triethylamine, pyridine, and benzenethiol. Claim 17 A step of supplying an indium precursor gas to a chamber to adsorb indium onto a substrate; a step of treating the substrate with a first hydrogen plasma; a step of supplying a selenium precursor gas to the chamber along with a hydrogen supply gas to react with the indium to form an indium-selenium compound; a step of supplying an indium precursor gas to the chamber to adsorb indium onto the substrate; a step of treating the substrate with a second hydrogen plasma; A method for forming an indium-selenium-tellurium layer using atomic layer deposition, comprising the step of supplying a tellurium precursor gas together with a hydrogen providing gas to the chamber to react with the indium to form an indium-tellurium compound, and thereby forming an indium-selenium-tellurium layer by a combination of the indium-selenium compound and the indium-tellurium compound, wherein, by the first and second hydrogen plasma treatments, the indium oxide formed from the indium precursor gas is formed into an indium hydride, the selenium precursor gas reacts with the hydrogen providing gas to form a selenium hydride, the tellurium precursor gas reacts with the hydrogen providing gas to form a tellurium hydride, and the indium hydride reacts with the selenium hydride and the tellurium hydride to form the indium-selenium-tellurium layer. Claim 18 A step of supplying an indium precursor gas to a chamber to adsorb indium onto a substrate; a step of treating the substrate with a first hydrogen plasma; a step of supplying a tellurium precursor gas to the chamber along with a hydrogen supply gas to react with the indium to form an indium-tellurium compound; a step of supplying an indium precursor gas to the chamber to adsorb indium onto a substrate; a step of treating the substrate with a second hydrogen plasma; A method for forming an indium-selenium-tellurium layer using atomic layer deposition, comprising the step of supplying a selenium precursor gas together with a hydrogen providing gas to the chamber to react with the indium to form an indium-selenium compound, and thereby forming an indium-selenium-tellurium layer by a combination of the indium-tellurium compound and the indium-selenium compound, wherein, by the first and second hydrogen plasma treatments, the indium oxide formed from the indium precursor gas is formed into an indium hydride, the selenium precursor gas reacts with the hydrogen providing gas to form a selenium hydride, the tellurium precursor gas reacts with the hydrogen providing gas to form a tellurium hydride, and the indium hydride reacts with the selenium hydride and the tellurium hydride to form the indium-selenium-tellurium layer. Claim 19 Formed by a method for forming an indium-selenium-tellurium layer using an atomic layer deposition method according to any one of claims 1, 6 to 18, and In x (Se, Te) 1-x Indium-selenium-tellurium layer having the chemical formula (0.1 ≤ x ≤ 0.9).

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