Resistive random access memory device and manufacturing method thereof

Abstract

The present disclosure relates to a resistance change memory device and a method for manufacturing the same. By stacking three or more halide perovskite resistance change layers having different compositions and / or dimensional structures between adjacent halide perovskite resistance change layers, a resistance change memory device with significantly improved durability and the ability to retain data for a long time can be realized.

Description

Technology Field

[0001] The present disclosure relates to a resistance change memory device comprising multiple resistance change layers and a method for manufacturing the same. Background Technology

[0002] Resistive change memory devices are attracting attention as one of the next-generation non-volatile memory devices due to their characteristics such as low power consumption, ultra-high speed, non-volatility, and simple structure. Resistive change memory devices have the advantage of being able to record information based on the resistance state by raising or lowering electrical resistance through electrical signals, and can utilize a simple device structure. In addition, when appropriate voltage / current conditions are applied, the resistance can be changed from a state of high resistance that does not conduct to a state where the resistance decreases and conducts.

[0003] Resistance switching memory devices have a structure in which upper and lower electrodes are arranged on a thin film, and a resistance switching layer made of an oxide thin film is included between the upper and lower electrodes. In this case, various materials are used as the resistance switching layer considering the bonding strength with the electrodes and the driving force, and recently, research using halide perovskites as the resistance switching layer is being conducted.

[0004] Conventionally, when perovskites are used as resistance change layers, they are formed by spin-coating precursors in which organic halide compounds such as CH3NH3X and metal-halogen compounds of the BX2 type are dissolved in a polar aprotic solvent. However, the resistance change layer formed by the above method has a disadvantage in that when a halide perovskite thin film with a different composition and dimensional structure is formed on the perovskite thin film, the perovskite thin film dissolves due to the polar aprotic solvent, thereby hindering the movement of ions between the resistance change layers. Therefore, research on various fabrication methods is necessary to realize memory devices comprising resistance change layers formed by stacking multiple layers of perovskite thin films. The problem to be solved

[0006] One embodiment aims to provide a resistance change memory device comprising: a first electrode on a substrate; a multi-resistance change layer formed by stacking a halide perovskite resistance change layer on the first electrode; and a second electrode formed on the multi-resistance change layer, wherein the multi-resistance change layer comprises a first resistance change layer formed on the first electrode, a second resistance change layer formed on the first resistance change layer, and one or more resistance change layers formed on the second resistance change layer.

[0007] Another embodiment aims to provide a method for manufacturing the above-mentioned resistance change memory device. means of solving the problem

[0008] One embodiment includes a first electrode on a substrate; a multi-resistance change layer formed by stacking a halide perovskite resistance change layer on the first electrode; and a second electrode formed on the multi-resistance change layer.

[0009] The above multiple resistance change layer provides a resistance change memory device comprising a first resistance change layer formed on a first electrode, a second resistance change layer formed on the first resistance change layer, and one or more resistance change layers formed on the second resistance change layer.

[0010] In one embodiment, each resistance change layer of the multiple resistance change layers comprises a halide perovskite that differs from an adjacent resistance change layer in at least one of its composition and dimensional structure, and the halide perovskite may be represented by the following chemical formula 1 or chemical formula 2.

[0011] [Chemical Formula 1]

[0012] RMX3

[0013] [Chemical Formula 2]

[0014] R2MX4

[0015] The above R is C 1-24The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion.

[0016] In one embodiment, the first resistance change layer may include a halide perovskite with a three-dimensional structure represented by the following chemical formula 1.

[0017] [Chemical Formula 1]

[0018] RMX3

[0019] The above R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion.

[0020] In one embodiment, the second resistance change layer may include a halide perovskite with a two-dimensional structure represented by the following chemical formula 2.

[0021] [Chemical Formula 2]

[0022] R2MX4

[0023] The above R is C 1-24The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion.

[0024] In one embodiment, one or more resistance change layers formed on the second resistance change layer include an n-th resistance change layer formed on the n-1-th resistance change layer, wherein the n-th resistance change layer includes a halide perovskite that differs from the n-1-th resistance change layer in at least one of its composition and dimensional structure, and wherein n is 3 or more, and the halide perovskite may be represented by the following chemical formula 1 or chemical formula 2.

[0025] [Chemical Formula 1]

[0026] RMX3

[0027] [Chemical Formula 2]

[0028] R2MX4

[0029] The above R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion.

[0030] In one embodiment, the resistance change memory device may further include a polymer protective layer.

[0031] In one embodiment, the polymer protective layer may comprise one or more ion-conducting polymers selected from the group consisting of polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polydimethylsiloxane, polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethyleneimine, polyphenylene terephthalamide, polymethoxypolyethylene glycol methacrylate, poly 2-methoxyethylglycidyl ether, and combinations thereof.

[0032] In one embodiment, the first electrode and the second electrode may each independently comprise a material selected from the group consisting of metals, conductive polymers, carbon materials, and combinations thereof.

[0033] In one embodiment, the thickness of the multi-resistance change layer may be 400 nm to 5 μm.

[0034] Another embodiment comprises the steps of: forming a first electrode on a substrate; stacking a halide perovskite resistance change layer on the first electrode to form a multi-resistance change layer; and forming a second electrode on the multi-resistance change layer.

[0035] The step of forming the multiple resistance change layers comprises: forming a first resistance change layer on a first electrode; forming a second resistance change layer on the first resistance change layer; and forming one or more resistance change layers on the second resistance change layer; thereby providing a method for manufacturing a resistance change memory device.

[0036] In one embodiment, the step of forming the multiple resistance change layers includes the step of stacking resistance change layers such that one or more of the composition and dimensional structure of adjacent halide perovskite resistance change layers are different, and the halide perovskite may be represented by the following chemical formula 1 or chemical formula 2.

[0037] [Chemical Formula 1]

[0038] RMX3

[0039] [Chemical Formula 2]

[0040] R2MX4

[0041] The above R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion.

[0042] In one embodiment, the step of forming the first resistance change layer may include the step of coating a solution in which a halide perovskite represented by the following chemical formula 1 is dissolved in a first solvent onto a first electrode.

[0043] [Chemical Formula 1]

[0044] RMX3

[0045] The above R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion.

[0046] In one embodiment, the first solvent may comprise one or more aprotic solvents selected from the group consisting of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, N-methyl-2-pyridine, pyridine, aniline, and combinations thereof.

[0047] In one embodiment, the step of forming the second resistance change layer may include the step of forming a halide perovskite represented by the following chemical formula 2 by coating a solution in which an organic halide is dissolved in a second solvent onto the first resistance change layer.

[0048] [Chemical Formula 2]

[0049] R2MX4

[0050] The above R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion.

[0051] In one embodiment, the second solvent may include a protonic solvent comprising a branched alcohol having 3 to 6 carbon atoms.

[0052] In one embodiment, the step of forming one or more resistance change layers on the second resistance change layer includes the step of forming an n-th resistance change layer on the n-1-th resistance change layer, wherein the n-th resistance change layer comprises a halide perovskite that differs from the n-1-th resistance change layer in at least one of its composition and dimensional structure, and wherein n is 3 or more, and the halide perovskite may be represented by the following chemical formula 1 or chemical formula 2.

[0053] [Chemical Formula 1]

[0054] RMX3

[0055] [Chemical Formula 2]

[0056] R2MX4

[0057] The above R is C 1-24The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion.

[0058] In one embodiment, the step of forming the n-th resistance change layer comprises: a step of forming a metal compound layer by depositing a metal compound (MX2) on the n-1-th resistance change layer using a thermal deposition apparatus; and a step of coating a solution in which an organic halide (RX) is dissolved in a second solvent onto the metal compound layer; wherein n is 3 or more, M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and X is a halide anion or a chalcogenide anion, and the second solvent may include a protionic solvent comprising a branched alcohol having 3 to 6 carbon atoms. Effects of the invention

[0060] A resistance change memory device according to one embodiment includes a multi-resistance change layer formed by stacking a halide perovskite resistance change layer adjacent between a first electrode and a second electrode and three or more halide perovskite resistance change layers having different compositions and / or dimensional structures, thereby significantly improving durability and allowing data to be retained for a long time.

[0061] A method for manufacturing a resistance change memory device according to another embodiment has the advantage of being able to be implemented by repeating a simple and simple process by including the step of forming a halide perovskite resistance change layer having a different composition and / or dimensional structure from an adjacent resistance change layer through thermal deposition. Brief explanation of the drawing

[0063] FIG. 1 is a cross-sectional view of a resistance change memory device according to one embodiment. Figure 2 is an XRD graph of a resistance change memory device according to an example and a comparative example. Figures 3 (a), (b), and (c) are SEM images of resistance change memory devices according to Comparative Example 1, Comparative Example 2, and Example, respectively. Figures 4 (a), (b), and (c) are graphs measuring the durability of resistance change memory devices according to Comparative Example 1, Comparative Example 2, and the Example, respectively. Figures 5(a), (b), and (c) are graphs measuring the data retention ability of resistance change memory devices according to Comparative Example 1, Comparative Example 2, and the Example, respectively. Specific details for implementing the invention

[0064] Since the embodiments described in this specification may be modified in various different forms, the technology according to one embodiment is not limited to the embodiments described below. Furthermore, throughout the specification, the terms "comprising," "including," "containing," "containing," or "having" any component do not exclude other components but may include additional components unless specifically stated otherwise, and do not exclude elements, materials, or processes not additionally listed.

[0065] The numerical ranges used herein include lower and upper limits and all values ​​within those ranges, increments logically derived from the form and width of the defined ranges, all of which are limited, and all possible combinations of upper and lower limits of numerical ranges limited in different forms. For example, if the content of the composition is limited to 10% to 80% or 20% to 50%, the numerical ranges of 10% to 50% or 50% to 80% should also be interpreted as being described in this specification. Unless otherwise specifically defined in this specification, values ​​outside the numerical range that may occur due to experimental error or rounding of values ​​are also included in the defined numerical ranges.

[0066] Unless otherwise specifically defined in this specification, “about” may be considered as a value within 30%, 25%, 20%, 15%, 10%, 5%, 3%, 2%, 1%, or 0.5% of the specified value.

[0067] In this specification, when a member is described as being located "on," "on top," "on top," "under," "on bottom," or "on bottom" of another member, this includes not only cases where a member is in contact with another member, but also cases where another member exists between the two members.

[0068] The term “alkyl group” in this specification means a monovalent straight-chain or broken-up saturated hydrocarbon group composed only of carbon and hydrogen atoms. Examples of such alkyl groups include, but are not limited to, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, t-butyl groups, pentyl groups, hexyl groups, etc.

[0069] The term “halogen group” in this specification means that a halogen atom belonging to Group 17 of the periodic table is included in a compound in the form of a functional group, and may be, for example, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), but is not limited thereto.

[0070] Hereinafter, the present disclosure will be described in detail (with reference to the attached drawings). However, this is merely illustrative and the present disclosure is not limited to the specific embodiments described illustratively.

[0072] One embodiment includes a first electrode on a substrate; a multi-resistance change layer formed by stacking a halide perovskite resistance change layer on the first electrode; and a second electrode formed on the multi-resistance change layer.

[0073] The above multiple resistance change layer provides a resistance change memory device comprising a first resistance change layer formed on a first electrode, a second resistance change layer formed on the first resistance change layer, and one or more resistance change layers formed on the second resistance change layer.

[0074] A resistance change memory device according to one embodiment includes one or more resistance change layers on a second resistance change layer, such that the uppermost resistance change layer of the multiple resistance change layers corresponds to the nth resistance change layer, wherein n is 3 or more. Specifically, the nth resistance change layer may be a third resistance change layer, a fourth resistance change layer, a fifth resistance change layer, or a sixth resistance change layer, but is not necessarily limited thereto.

[0075] In one embodiment, the resistance change memory device can significantly improve the durability of the memory device and maintain data for a long time by promoting ion movement between halide perovskite resistance change layers and suppressing filament growth.

[0076] In one embodiment, each resistance change layer of the multiple resistance change layers comprises a halide perovskite that differs from an adjacent resistance change layer in at least one of its composition and dimensional structure, and the halide perovskite may be represented by the following Chemical Formula 1 or Chemical Formula 2. In this case, the halide perovskite represented by Chemical Formula 1 has a three-dimensional crystal structure, and the halide perovskite represented by Chemical Formula 2 has a two-dimensional crystal structure.

[0077] [Chemical Formula 1]

[0078] RMX3

[0079] [Chemical Formula 2]

[0080] R2MX4

[0081] The above R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion.

[0082] In one embodiment, the R is (R1R2R3R4N) + As a monovalent organic ammonium ion represented as, R1 to R4 are each independently C 1-24 The linear or branched alkyl group of, C 3-20 The cycloalkyl group of, C 6-20 It may include, but is not necessarily limited to, a group selected from the aryl group and combinations thereof.

[0083] In one embodiment, the R is (R5-NH3) + As a monovalent organic ammonium ion represented as, R5 is C 1-24 The linear or branched alkyl group of, C 3-20 The cycloalkyl group of, C6-20 It may include, but is not necessarily limited to, a group selected from the aryl group and combinations thereof.

[0084] In one embodiment, R is the chemical formula (R6R7N=CH-NR8R9) + It may be represented as, where R6 is hydrogen, unsubstituted or substituted C 1-20 It may be an alkyl group, or an unsubstituted or substituted aryl group, and R7 is hydrogen, an unsubstituted or substituted C 1-20 It may be an alkyl group, or an unsubstituted or substituted aryl group, and R8 is hydrogen, an unsubstituted or substituted C 1-20 It may be an alkyl group, or an unsubstituted or substituted aryl group, and R9 is hydrogen, an unsubstituted or substituted C 1-20 It may be an alkyl group, or an unsubstituted or substituted aryl group, but is not necessarily limited thereto.

[0085] Specifically, the above R1 to R 10 Each can independently be an alkyl group, and these alkyl groups are C 1-24 , C 1-20 , C 1-10 , C 1-8 , C 1-5 , or C 1-3It represents a linear or branched alkyl group, and when the alkyl group is substituted with an alkyl group, it is also used interchangeably as "branched alkyl group." Substituents that can be substituted on the alkyl group include at least one selected from the group consisting of halo (e.g., F, Cl, Br, I), haloalkyl (e.g., CCl3 or CF3), alkoxy, alkylthio, hydroxy, carboxyl (-C(O)-OH), alkyloxycarbonyl (-C(O)-OR), alkylcarbonyloxy (-OC(O)-R), amino (-NH2), carbamoyl (-C(O)-NHR), urea (-NH-C(O)-NHR-), and thiol (-SH), but are not limited thereto. In addition, among the alkyl groups described above, the alkyl group having two or more carbon atoms may include at least one carbon-to-carbon double bond or at least one carbon-to-carbon triple bond, but is not limited thereto. For example, it may include methyl, ethyl, propyl, butyl, pentyl, hexyl, hepyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosanyl, or all possible isomers thereof, but is not limited thereto. For example, the alkyl groups that may be substituted for each of R1 to R4 and R5, or independently of each other, C 1-10 The alkyl group of, i.e., may be a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or decyl group, or C 1-6 The alkyl group of, i.e., may be a methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group, or C 1-4 The alkyl group of may be a methyl group, an ethyl group, an i-propyl group, an n-propyl group, a t-butyl group, an s-butyl group, or an n-butyl group, but is not necessarily limited thereto.

[0086] When the above alkyl group is substituted, the substituents substituting the alkyl group may be one, two, or three, but are not limited thereto. The above R1 to R 10 Among the substituents described independently for each, the aryl group is a substituted or unsubstituted aromatic group of a single or double ring, which may comprise 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms in the aromatic ring portion. For example, the aryl groups used herein may include, but are not limited to, phenyl groups, naphthyl groups, indenyl groups, and indanyl groups. The aryl group may be substituted or unsubstituted; if the aryl group defined above is substituted, the substituent may be one or more substituents selected from, but are not limited to. Unsubstituted C 1-6 alkyl group (forming an aralkyl group), unsubstituted aryl group, cyano group, amino group, C 1-10 The alkylamino group of, C 1-10 of dialkylamino group, arylamino group, diarylamino group, arylalkylamino group, amino group, amide group, hydroxyl group, halogen group, carboxyl group, ester group, acyl group, acyloxyl group, C 1-20 alkoxy groups, aryloxy groups, haloalkyl groups, sulfhydryl groups (i.e., thiols, -SH), C 1-10 The alkylthio group, arylthio group, sulfonic acid group, phosphate group, phosphate ester group, phosphonic acid group, and sulfonyl group may be included, but are not limited thereto. For example, the substituted aryl group may have one, two, or three substituents, but is not limited thereto. For example, the substituted aryl group may have a single alkylene group having 1 to 6 carbon atoms, or the formula [-X-(C 1-6 alkylene)], or chemical formula [-X-(C 1-6It can be substituted at two positions with a two-coordination group represented as [alkylene)-X-], where X can be selected from O, S, and NR, and R is H, an aryl group, or C 1-6It may be an alkyl group. For example, the substituted aryl group may be a cycloalkyl group or an aryl group fused with a heterocyclic group. For example, the cyclic atoms of the aryl group may include one or more heteroatoms as a heteroaryl group. Such an aryl group or heteroaryl group is a substituted or unsubstituted single or double cyclic heterocyclic aromatic group, and said aromatic group may include 6 to 10 atoms in a cyclic portion containing one or more heteroatoms. For example, as a 5- or 6-part split ring, it may include at least one heteroatom selected from O, S, N, P, Se, and Si. For example, said heteroatoms may include 1, 2, or 3. For example, the heteroaryl group may include, but is not limited to, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a furanyl group, a thienyl group, a pyrazolidinyl group, a pyrrolyl group, an oxazolyl group, an oxadiazolyl group, an isoxazolyl group, a thiadiazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, a quinolyl group, and an isoquinolyl group. For example, the heteroaryl group may not be substituted, or it may be substituted as previously explained for the aryl group, and if it is substituted, the substituents may be, for example, 1, 2, or 3, but are not necessarily limited thereto.

[0087] In addition, the above R may include an alkali metal cation in addition to the organic cation, that is, may include a mixed cation of the organic cation and the alkali metal cation, but is not necessarily limited thereto. In this case, the molar ratio of the alkali metal cation among the total cations of R in Formula 1 may be greater than 0 and less than or equal to 0.2, but is not necessarily limited thereto. The alkali metal cation may include a cation of a metal selected from the group consisting of Cs, K, Rb, Mg, Ca, Sr, Ba, and combinations thereof, but is not necessarily limited thereto.

[0088] In one embodiment, X may include a halide anion or a chalcogenide anion, but is not necessarily limited thereto. Specifically, X may include one or two or more anions, and may include one or more halide anions or one or more chalcogenide anions, or a mixture thereof. Additionally, X is F - , Cl - , Br - , I - , S 2- , Se 2- . Te 2- It may include, but is not necessarily limited to, those selected from the group consisting of , and combinations thereof. For example, X is a monovalent halide anion, F - , Cl - , Br - , I - It may comprise one or more anions selected from the group consisting of , and combinations thereof, wherein X is a divalent chalcogenide anion, and S 2- , Se 2- . Te 2-It may include one or more anions selected from the group consisting of , and combinations thereof, but is not necessarily limited thereto.

[0089] In one embodiment, the three-dimensional halide perovskite represented by Chemical Formula 1 is CH3NH3PbI x Cl y (real numbers 0≤x≤3, real numbers 0≤y≤3, and x+y=3), CH3NH3PbI x Br y (real numbers 0≤x≤3, real numbers 0≤y≤3, and x+y=3), CH3NH3PbCl x Br y (real numbers 0≤x≤3, real numbers 0≤y≤3, and x+y=3), and CH3NH3PbI x F y One or more may be selected from (real numbers 0≤x≤3, real numbers 0≤y≤3, and x+y=3), and also, (CH3NH3)2PbI x Cl y (real numbers 0≤x≤4, real numbers 0≤y≤4 and x+y=4), (CH3NH3)2PbI x Br y (real numbers 0≤x≤4, real numbers 0≤y≤4 and x+y=4), (CH3NH3)2PbCl x Br y (real numbers 0≤x≤4, real numbers 0≤y≤4 and x+y=4), and (CH3NH3)2PbI x F y It may be one or more selected from (real numbers 0≤x≤4, real numbers 0≤y≤4, and x+y=4).

[0090] 구체적으로, 상기 화학식 1로 표시되는 3차원 구조의 할라이드 페로브스카이트는 CH3NH3PbI3(이하, MAPbI3라고도 함), CH3NH3PbBr3(이하, MAPbBr3라고도 함), CH3NH3PbCl3, CH3NH3PbF3, CH3NH3PbBrI2, CH3NH3PbBrCl2, CH3NH3PbIBr2, CH3NH3PbICl2, CH3NH3PbClBr2, CH3NH3PbI2Cl, CH3NH3SnBrI2, CH3NH3SnBrCl2, CH3NH3SnF2Br, CH3NH3SnIBr2, CH3NH3SnICl2, CH3NH3SnF2I, CH3NH3SnClBr2, CH3NH3SnI2Cl, CH3NH3SnF2Cl, CH3CH2NH3PbI3, CH3CH2NH3PbBr3, CH3CH2NH3PbCl3, CH3CH2NH3PbF3, CH3CH2NH3PbBrI2, CH3CH2NH3PbBrCl2, CH3CH2NH3PbIBr2, CH3CH2NH3PbICl2, CH3CH2NH3PbClBr2, CH3CH2NH3PbI2Cl, CH3CH2NH3SnBrI2, CH3CH2NH3SnBrCl2, CH3CH2NH3SnF2Br, CH3CH2NH3SnIBr2, CH3CH2NH3SnICl2, CH3CH2NH3SnF2I, CH3CH2NH3SnClBr2, CH3CH2NH3SnI2Cl, CH3CH2NH3SnF2Cl, CH3(CH2)2NH3PbI3, CH3(CH2)2NH3PbBr3, CH3(CH2)2NH3PbCl3, CH3(CH2)2NH3PbF3, CH3(CH2)2NH3PbBrI2, CH3(CH2)2NH3PbBrCl2, CH3(CH2)2NH3PbIBr2, CH3(CH2)2NH3PbICl2, CH3(CH2)2NH3PbClBr2, CH3(CH2)2NH3PbI2Cl, CH3(CH2)2NH3SnF2Br, CH3(CH2)2NH3SnICl2, CH3(CH2)2NH3SnF2I, CH3(CH2)2NH3SnI2Cl, CH3(CH2)2NH3SnF2Cl, CH3(CH2)3NH3PbI3, CH3(CH2)3NH3PbBr3,It may be one or more selected from the group consisting of CH3(CH2)3NH3PbCl3, CH3(CH2)3NH3PbF3, CH3(CH2)3NH3PbBrI2, CH3(CH2)3NH3PbBrCl2, CH3(CH2)3NH3PbIBr2, CH3(CH2)3NH3PbICl2, CH3(CH2)3NH3PbClBr2, CH3(CH2)3NH3PbI2Cl, CH3(CH2)3NH3SnF2Br, CH3(CH2)3NH3SnF2I, and CH3(CH2)3NH3SnF-Cl, but is not necessarily limited thereto. For example, the first resistance change layer may include CH3NH3PBI3.

[0091] In one embodiment, the first resistance change layer may include a halide perovskite with a three-dimensional structure represented by the following chemical formula 1.

[0092] [Chemical Formula 1]

[0093] RMX3

[0094] The above R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. At this time, regarding the R, M, X and the three-dimensional halide perovskite represented by Formula 1, the description regarding the R, M, X and the three-dimensional halide perovskite represented by Formula 1 described above can be applied in the same way, so the redundant description below is omitted.

[0095] In one embodiment, the second resistance change layer may include a halide perovskite with a two-dimensional structure represented by the following chemical formula 2.

[0096] [Chemical Formula 2]

[0097] R2MX4

[0098] The above R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. In this case, regarding R, M, and X, the descriptions regarding R, M, and X described above can be applied in the same way, so duplicate descriptions below are omitted.

[0099] In one embodiment, the second resistance change layer may include (PEA)2PBI4.

[0100] In one embodiment, one or more resistance change layers formed on the second resistance change layer include an n-th resistance change layer formed on the n-1-th resistance change layer, wherein the n-th resistance change layer includes a halide perovskite that differs from the n-1-th resistance change layer in at least one of its composition and dimensional structure, and wherein n is 3 or more, and the halide perovskite may be represented by the following chemical formula 1 or chemical formula 2.

[0101] [Chemical Formula 1]

[0102] RMX3

[0103] [Chemical Formula 2]

[0104] R2MX4

[0105] The above R is C 1-24The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. At this time, regarding R, M, X, the halide perovskite represented by Formula 1 and the halide perovskite represented by Formula 2, the descriptions regarding R, M, X, the halide perovskite represented by Formula 1 and the halide perovskite represented by Formula 2 described above can be applied in the same way, so duplicate descriptions below are omitted.

[0106] In one embodiment, the resistance change memory device comprises a multi-resistance change layer including a halide perovskite that differs from an adjacent resistance change layer in at least one of its composition and dimensional structure, thereby significantly improving durability compared to a conventional resistance change memory device and allowing data to be retained for a long time.

[0107] In one embodiment, the resistance change memory device may further include a polymer protective layer.

[0108] In one embodiment, the polymer protective layer may comprise one or more ion-conducting polymers selected from the group consisting of polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polydimethylsiloxane, polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethyleneimine, polyphenylene terephthalamide, polymethoxypolyethylene glycol methacrylate, poly 2-methoxyethylglycidyl ether, and combinations thereof, but is not necessarily limited thereto. For example, the polymer protective layer may comprise polymethyl methacrylate.

[0109] In one embodiment, the first electrode and the second electrode may each independently comprise a material selected from the group consisting of metals, conductive polymers, carbon materials, and combinations thereof. Specifically, the metal may include a metal selected from the group consisting of Pt, Ti, Cu, Ni, Sc, V, Cr, Mn, Fe, Co, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Au, Hg, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Cn, and combinations thereof, and the conductive polymer may include a material selected from the group consisting of poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate, polyacetylene, polypyrrole, polythiophene, polyaniline, polyphenylene, polyphenylene sulfide, polyfullerene, and combinations thereof, and the carbon material may include a carbon material selected from the group consisting of carbon nanotubes, graphene, fullerene, carbon nanofibers, and combinations thereof, but is not necessarily... It is not limited.

[0110] In one embodiment, the thickness of the multi-resistance change layer may be 400 nm to 5 μm. Specifically, the thickness of the multi-resistance change layer may be 400 nm to 4 μm or 450 nm to 3 μm, but is not necessarily limited thereto. If the thickness of the multi-resistance change layer is less than 400 nm or greater than 5 μm, the stability of the resistance change memory device may be reduced. Specifically, if the thickness of the multi-resistance change layer becomes thinner than 400 nm, the increase in local electric field strength may accelerate filament growth within the resistance change layer, thereby reducing the durability or stability of the resistance change memory device.

[0111] Another embodiment comprises the steps of: forming a first electrode on a substrate; stacking a halide perovskite resistance change layer on the first electrode to form a multi-resistance change layer; and forming a second electrode on the multi-resistance change layer.

[0112] The step of forming the multiple resistance change layer comprises: forming a first resistance change layer on a first electrode; forming a second resistance change layer on the first resistance change layer; and forming one or more resistance change layers on the second resistance change layer; thereby providing a method for manufacturing a resistance change memory device. At this time, regarding the first electrode, the multiple resistance change layer, and the second electrode, the descriptions regarding the first electrode, the multiple resistance change layer, and the second electrode described above can be applied identically, so duplicate descriptions below are omitted.

[0113] In one embodiment, the step of forming the multiple resistance change layers includes the step of stacking resistance change layers such that one or more of the composition and dimensional structure of adjacent halide perovskite resistance change layers are different, and the halide perovskite may be represented by the following chemical formula 1 or chemical formula 2.

[0114] [Chemical Formula 1]

[0115] RMX3

[0116] [Chemical Formula 2]

[0117] R2MX4

[0118] The above R is C 1-24The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. At this time, regarding R, M, X, the halide perovskite represented by Formula 1 and the halide perovskite represented by Formula 2, the descriptions regarding R, M, X, the halide perovskite represented by Formula 1 and the halide perovskite represented by Formula 2 described above can be applied in the same way, so duplicate descriptions below are omitted.

[0119] In one embodiment, the step of forming the first resistance change layer may include the step of coating a solution in which a halide perovskite represented by the following chemical formula 1 is dissolved in a first solvent onto a first electrode.

[0120] [Chemical Formula 1]

[0121] RMX3

[0122] The above R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. At this time, regarding R, M, X and the halide perovskite represented by Formula 1, the descriptions regarding R, M, X and the halide perovskite represented by Formula 1 described above can be applied in the same way, so duplicate descriptions below are omitted.

[0123] In one embodiment, the coating may be performed by selecting from the group consisting of spin coating, bar coating, nozzle printing, spray coating, slot die coating, gravure printing, inkjet printing, screen printing, electrohydrodynamic jet printing, electrospray, and combinations thereof, but is not necessarily limited thereto. Specifically, the coating may be performed by spin coating.

[0124] Spin coating is a method of coating a thin layer of a solution onto a substrate by rotating the substrate at high speed, which allows for the rapid volatilization of the solvent. Additionally, spin coating offers the advantage of being beneficial when coating low-viscosity solutions.

[0125] In one embodiment, the first solvent may comprise one or more aprotic solvents selected from the group consisting of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, N-methyl-2-pyridine, pyridine, aniline, and combinations thereof, but is not necessarily limited thereto. Specifically, the first solvent may comprise dimethylformamide and dimethyl sulfoxide.

[0126] In one embodiment, the step of forming the second resistance change layer may include the step of forming a halide perovskite represented by the following chemical formula 2 by coating a solution in which an organic halide is dissolved in a second solvent onto the first resistance change layer. Specifically, a portion of the halide perovskite on the first resistance change layer may be melted by the second solvent to form a halide perovskite represented by the following chemical formula 2. At this time, since the description regarding the coating described above can be applied identically to the coating, the following redundant description is omitted.

[0127] [Chemical Formula 2]

[0128] R2MX4

[0129] The above R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. At this time, regarding R, M, X and the halide perovskite represented by Formula 2, the descriptions regarding R, M, X and the halide perovskite represented by Formula 2 described above can be applied in the same way, so duplicate descriptions below are omitted.

[0130] In one embodiment, the organic halide may be selected from PhEtNH3I, MeNH3I, PhEtNH3Cl, MeNH3Cl, PhEtNH3Br, MeNH3Br, and combinations thereof, but is not necessarily limited thereto. Specifically, the organic halide may include PhEtNH3I.

[0131] In one embodiment, the second solvent may include a protic solvent comprising a branched alcohol having 3 to 6 carbon atoms, but is not necessarily limited thereto. Specifically, the second solvent may include isopropyl alcohol. If a non-protic solvent is used as the second solvent, the perovskite on the first resistance change layer is completely dissolved, so a junction structure in which a second resistance change layer is formed thereon cannot be formed.

[0132] In one embodiment, the step of forming one or more resistance change layers on the second resistance change layer includes the step of forming an n-th resistance change layer on the n-1-th resistance change layer, wherein the n-th resistance change layer comprises a halide perovskite that differs from the n-1-th resistance change layer in at least one of its composition and dimensional structure, and wherein n is 3 or more, and the halide perovskite may be represented by the following chemical formula 1 or chemical formula 2.

[0133] [Chemical Formula 1]

[0134] RMX3

[0135] [Chemical Formula 2]

[0136] R2MX4

[0137] The above R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. At this time, regarding R, M, X, the halide perovskite represented by Formula 1 and the halide perovskite represented by Formula 2, the descriptions regarding R, M, X, the halide perovskite represented by Formula 1 and the halide perovskite represented by Formula 2 described above can be applied in the same way, so duplicate descriptions below are omitted.

[0138] In one embodiment, the step of forming the n-th resistance change layer comprises: a step of forming a metal compound layer by depositing a metal compound (MX2) on the n-1-th resistance change layer using a thermal deposition apparatus; and a step of coating a solution in which an organic halide (RX) is dissolved in a second solvent onto the metal compound layer; wherein n is 3 or more, M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and R is C 1-24 The alkyl group is substituted or unsubstituted, and when R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, and X is a halide anion or a chalcogenide anion, and the second solvent may include a protionic solvent comprising a branched alcohol having 3 to 6 carbon atoms. In this case, regarding R, M, X, the coating, and the organic halide, the descriptions regarding R, M, X, the coating, and the organic halide described above can be applied in the same way, so duplicate descriptions below are omitted.

[0139] In one embodiment, the step of forming the metal compound layer may include a thermal deposition step. The thermal deposition step may be performed by applying heat at a temperature of 50°C to 250°C for 1 to 2 hours, but is not necessarily limited thereto.

[0140] When a halide perovskite resistance change layer with a different composition and / or dimensional structure is stacked on a halide perovskite resistance change layer, ion movement is suppressed and filament growth cannot be controlled due to electrical repulsion between halide perovskite ions contained in adjacent resistance change layers, so conventional resistance change memory devices have a problem of poor durability and stability.

[0141] On the other hand, in one embodiment of the present disclosure, by forming a metal compound layer through a thermal deposition process when forming the n-th resistance change layer, the electrical repulsion between the halide perovskite ions of the n-th resistance change layer and the halide perovskite ions of the adjacent n-1-th resistance change layer is weakened. Therefore, since the method for manufacturing a resistance change memory device according to one embodiment can promote ion movement between adjacent resistance change layers, the resistance change memory device can have multiple resistance change layers stably stacked compared to conventional resistance change memory devices, thereby significantly improving durability and allowing data to be retained for a long time.

[0142] In one embodiment, after forming the n-th resistance change layer, impurities can be removed by spin-coating a cleaning solution onto the n-th resistance change layer.

[0143] In one embodiment, the method for manufacturing the resistance change memory device may further include the step of forming a polymer protective layer on the n-th resistance change layer after forming the multiple resistance change layers. Specifically, the method for forming the polymer protective layer may include the step of spin-coating an ion-conducting polymer selected from the group consisting of polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polydimethylsiloxane, polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethyleneimine, polyphenylene terephthalamide, polymethoxypolyethylene glycol methacrylate, poly2-methoxyethylglycidyl ether, and combinations thereof onto the n-th resistance change layer, but is not necessarily limited thereto. For example, the method for forming the polymer protective layer may include the step of spin-coating polymethyl methacrylate onto the n-th resistance change layer.

[0144] In one embodiment, the method for manufacturing the resistance change memory device may include the step of forming a second electrode on the polymer protective layer.

[0145] In the following, embodiments are further described with reference to specific experimental examples. The embodiments and comparative examples included in the experimental examples are merely illustrative of one embodiment and do not limit the appended claims. It is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope and spirit of the present disclosure, and that such variations and modifications fall within the scope of the appended claims.

[0147] <Example> Manufacture of a resistance change memory device

[0148] First, hydrophilic groups were formed on the surface of a silicon substrate on which a Pt / Ti electrode (100) was deposited by UV ozone treatment. A mixed solution was prepared by dissolving CH3NH3I and PbI2 in a molar ratio of 1:1 in 55% by weight of dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) solvents, and then the prepared mixed solution was spin-coated onto the silicon substrate to form a first resistance change layer (200).

[0149] Next, a solution of PhEtNH3I dissolved in 20 mg / ml of isopropyl alcohol solvent was spin-coated onto the first resistance change layer to form a second resistance change layer (300).

[0150] Next, to deposit a PbI2 layer on the second resistance change layer using a thermal deposition apparatus, PbI21 g was deposited at 150 ℃ for 1 hour to 1 hour 30 minutes. Then, a solution of CH3NH3I dissolved in 20 mg / ml of isopropyl alcohol solvent was spin-coated onto the PbI2 layer to form a third resistance change layer (400).

[0151] Next, a solution of polymethyl methacrylate dissolved in 2 mg / ml of chlorobenzene was spin-coated onto the third resistance change layer to form a polymer protective layer (500).

[0152] Finally, 10 -6A second electrode (600) was formed by depositing silver (Ag) at least 50 nm on the polymer protective layer under torr conditions. FIG. 1 shows a cross-sectional view of a resistance change memory device according to an embodiment.

[0154] <Comparative Example 1> Manufacture of a resistance change memory device

[0155] In the example, a resistance change memory device was manufactured in the same manner as in the example, except for the step of forming a second resistance change layer and a third resistance change layer.

[0156] <Comparative Example 2> Manufacture of a Resistance Change Memory Device

[0157] A resistance change memory device was manufactured in the same manner as in the example, except for the step of forming a third resistance change layer.

[0159] X-ray diffraction (XRD) patterns were measured to analyze the resistance change layer of the resistance change memory device according to the above examples and comparative examples (Fig. 2). Since the resistance change memory devices according to the examples and comparative examples show differences in intensity values ​​due to X-ray absorption and scattering of the resistance change layer, the resistance change layer can be analyzed through the XRD graph according to Fig. 2. Accordingly, it can be confirmed that the resistance change memory device according to the example includes a first resistance change layer, a second resistance change layer, and a third resistance change layer, whereas Comparative Example 1 includes a first resistance change layer, and Comparative Example 2 includes a first resistance change layer and a second resistance change layer.

[0160] In addition, a scanning electron microscope (SEM) was used to show the side view of the resistance change memory device according to the above example and comparative example (Fig. 3). Fig. 3 (a), (b), and (c) are SEM images of the resistance change memory device according to Comparative Example 1, Comparative Example 2, and the example, respectively, and it can be seen that the resistance change layer thickness of the resistance change memory device according to the comparative example is 350 nm, whereas the resistance change layer thickness of the example is 500 nm.

[0162] <Experimental Example 1> Measurement of Durability of Resistance Change Memory Device

[0163] To measure the durability of the resistance change memory device according to the examples and comparative examples, the change in resistance value was measured using a Keithley 4200 Semiconductor analyzer (Fig. 4). The specific measurement method is as follows.

[0164] The number of repeated operation cycles was measured through a write / erase system by varying the DC voltage in the order of 1 V (write), 0.05 V (read), -1 V (erase), and 0.05 V (read). At this time, the change in resistance value according to the current flow is shown in Fig. 4. Looking at Fig. 4, Comparative Examples 1 and 2 ceased operation after the device lifespan ended at 500 cycles or more, whereas the Example maintained a steady device lifespan even after 2000 cycles or more, indicating that the durability of the Example is significantly superior to that of the Comparative Examples.

[0165] Meanwhile, the durability of the resistance change memory device is related to the thickness of the resistance change layer. When comparing the thickness of the resistance change layer measured in Fig. 3, it can be seen that the resistance change layer thickness of the comparative example is 350 nm, which is thinner than the resistance change layer thickness (500 nm) of the example. Therefore, since the resistance change memory device of the example can form a thick resistance change layer, filament growth is suppressed even when the electric field strength increases, thereby improving the durability of the memory device.

[0167] <Experimental Example 2> Measurement of Data Retention Capability of Resistance Change Memory Device

[0168] To measure the data retention capability of the resistance change memory device according to the examples and comparative examples, the change in resistance value was measured using a Keithley 4200 Semiconductor analyzer. The specific measurement method is as follows.

[0169] After measuring the change in resistance value (on) by changing the DC voltage to 1 V (write) and 0.05 V (read it mode) for 10,000 seconds, the change in resistance value (off) was measured by changing the DC voltage to 1 V (erase) and 0.05 V (read it mode) for 10,000 seconds, and the results are shown in FIG. 5. Looking at FIG. 5, it can be confirmed that the resistance value of the embodiment remains constant during the time measured in the on state. Therefore, the resistance change memory device according to the embodiment can retain data for a period of time of 10,000 seconds or more.

[0171] The above description is merely an example of applying the principles of the present disclosure, and other configurations may be further included without departing from the scope of the present disclosure. Although one embodiment has been described in detail through examples and experimental examples, the scope of one embodiment is not limited to specific embodiments and should be interpreted according to the appended claims. Explanation of the symbols

[0172] 100: First electrode 200: First resistance change layer 300: Second resistance change layer 400: Third resistance change layer 500: Polymer protective layer 600: Second electrode

Claims

Claim 1 A resistance change memory device comprising: a first electrode on a substrate; a multi-resistance change layer formed by stacking a halide perovskite resistance change layer on the first electrode; and a second electrode formed on the multi-resistance change layer; wherein the multi-resistance change layer comprises a first resistance change layer formed on the first electrode, a second resistance change layer formed on the first resistance change layer, and one or more resistance change layers formed on the second resistance change layer, and each resistance change layer of the multi-resistance change layer comprises a halide perovskite having at least one composition and dimensional structure different from that of an adjacent resistance change layer. Claim 2 A resistance change memory device according to claim 1, wherein the halide perovskite is represented by the following chemical formula 1 or chemical formula 2. [Chemical Formula 1] RMX3 [Chemical Formula 2] R2MX4 (wherein R is C 1-24 is a substituted or unsubstituted alkyl group, wherein if R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, wherein M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. Claim 3 A resistance change memory device according to claim 1, wherein the first resistance change layer comprises a halide perovskite having a three-dimensional structure represented by the following chemical formula 1. [Chemical Formula 1] RMX3 (wherein R is C 1-24 is a substituted or unsubstituted alkyl group, wherein if R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, wherein M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. Claim 4 A resistance change memory device according to claim 1, wherein the second resistance change layer comprises a two-dimensional halide perovskite represented by the following chemical formula 2. [Chemical Formula 2] R2MX4 (wherein R is C 1-24 is a substituted or unsubstituted alkyl group, wherein if R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, wherein M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. Claim 5 A resistance change memory device according to claim 1, wherein one or more resistance change layers formed on the second resistance change layer comprise an n-th resistance change layer formed on the n-1 resistance change layer, wherein the n-th resistance change layer comprises a halide perovskite that differs from the n-1 resistance change layer in at least one of its composition and dimensional structure, wherein n is 3 or more, and the halide perovskite is represented by the following chemical formula 1 or chemical formula 2. [Chemical Formula 1] RMX3 [Chemical Formula 2] R2MX4 (wherein R is C 1-24 is a substituted or unsubstituted alkyl group, wherein if R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, wherein M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. Claim 6 In claim 1, the resistance change memory device further comprises a polymer protective layer. Claim 7 A resistance change memory device according to claim 6, wherein the polymer protective layer comprises one or more ion-conducting polymers selected from the group consisting of polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polydimethylsiloxane, polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethyleneimine, polyphenylene terephthalamide, polymethoxypolyethylene glycol methacrylate, poly 2-methoxyethylglycidyl ether, and combinations thereof. Claim 8 A resistance change memory device according to claim 1, wherein the first electrode and the second electrode each independently comprise a material selected from the group consisting of metals, conductive polymers, carbon materials, and combinations thereof. Claim 9 A resistance change memory device according to claim 1, wherein the thickness of the multiple resistance change layer is 400 nm to 5 μm. Claim 10 A step of forming a multi-resistance change layer comprising: forming a first electrode on a substrate; forming a first resistance change layer on the first electrode; forming a second resistance change layer on the first resistance change layer; and forming an n-1 resistance change layer on the n-1 resistance change layer; and a step of forming a second electrode on the multi-resistance change layer; wherein the n-1 resistance change layer comprises a halide perovskite that differs from the n-1 resistance change layer in at least one of its composition and dimensional structure, and n is 3 or more, and the step of forming the n-1 resistance change layer comprises: forming a metal compound layer by depositing a metal compound (MX2) on the n-1 resistance change layer using a thermal deposition apparatus; and coating a solution in which an organic halide (RX) is dissolved in a second solvent onto the metal compound layer; wherein M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and R is C 1-24 A method for manufacturing a resistance change memory device comprising a substituted or unsubstituted alkyl group, wherein if R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, wherein X is a halide anion or a chalcogenide anion, and the second solvent is a protic solvent comprising a C3-6 branched alcohol. Claim 11 A method for manufacturing a resistance change memory device according to claim 10, wherein the step of forming the multiple resistance change layers comprises the step of stacking resistance change layers such that one or more of the composition and dimensional structure of adjacent halide perovskite resistance change layers are different, and the halide perovskite is represented by the following chemical formula 1 or chemical formula 2. [Chemical Formula 1] RMX3 [Chemical Formula 2] R2MX4 (wherein R is C 1-24 is a substituted or unsubstituted alkyl group, wherein if R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, wherein M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. Claim 12 A method for manufacturing a resistance change memory device according to claim 10, wherein the step of forming the first resistance change layer comprises the step of coating a solution obtained by dissolving a halide perovskite represented by the following chemical formula 1 in a first solvent onto a first electrode. [Chemical Formula 1] RMX3 (wherein R is C 1-24 is a substituted or unsubstituted alkyl group, wherein if R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, wherein M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. Claim 13 A method for manufacturing a resistance change memory device according to claim 12, wherein the first solvent comprises one or more non-protic solvents selected from the group consisting of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, N-methyl-2-pyridine, pyridine, aniline, and combinations thereof. Claim 14 A method for manufacturing a resistance change memory device according to claim 10, wherein the step of forming the second resistance change layer comprises the step of coating a solution in which an organic halide is dissolved in a second solvent onto the first resistance change layer to form a halide perovskite represented by the following chemical formula 2. [Chemical Formula 2] R2MX4 (wherein R is C 1-24 is a substituted or unsubstituted alkyl group, wherein if R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, wherein M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. Claim 15 A method for manufacturing a resistance change memory device according to claim 14, wherein the second solvent comprises a protic solvent comprising a branched alcohol having 3 to 6 carbon atoms. Claim 16 A method for manufacturing a resistance change memory device according to claim 10, wherein the halide perovskite is represented by the following chemical formula 1 or chemical formula 2. [Chemical Formula 1] RMX3 [Chemical Formula 2] R2MX4 (wherein R is C 1-24 is a substituted or unsubstituted alkyl group, wherein if R is substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group, or a methoxy group, wherein M is a metal cation selected from the group consisting of Pb, Sn, Ge, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, and combinations thereof, and X is a halide anion or a chalcogenide anion. Claim 17 delete

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