KR101721162B1 - Proton-based resistive switching memory and method of fabricating the same - Google Patents

Proton-based resistive switching memory and method of fabricating the same Download PDF

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KR101721162B1
KR101721162B1 KR1020150040235A KR20150040235A KR101721162B1 KR 101721162 B1 KR101721162 B1 KR 101721162B1 KR 1020150040235 A KR1020150040235 A KR 1020150040235A KR 20150040235 A KR20150040235 A KR 20150040235A KR 101721162 B1 KR101721162 B1 KR 101721162B1
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resistance
layer
electrode layer
rare earth
nickel oxide
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KR20160113904A (en
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손준우
오차돌
허승양
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포항공과대학교 산학협력단
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    • H01L27/24—
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/26—Bombardment with radiation
    • H01L21/263—Bombardment with radiation with high-energy radiation
    • H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
    • H01L27/11507—
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01001—Hydrogen [H]

Abstract

The present invention provides a method of manufacturing a semiconductor device, comprising: forming a resistance variable layer; And a step of hydrogenating at least a portion of the resistance variable layer to have a property of being capable of metal-insulator transition from metal to insulator through hydrogen treatment, And a resistance change memory using hydrogen ion diffusion realized by using the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resistance change memory using hydrogen ion diffusion,

The present invention relates to a memory and a method of manufacturing the same, and more particularly, to a resistance change memory and a method of manufacturing the same.

Since the late 1900s, semiconductor memory applications have been increasingly used not only in PCs but also in various electronic devices. Demand for semiconductor devices has been rapidly increasing due to the development of semiconductor processing technology. Has been increasing year by year, as described in Moore's law and Hwang's law.

For the high integration of devices, much research has been done so far to reduce the size of devices. However, the physical limitations have been reached. Recently, studies have been actively carried out to improve the integration degree by changing conditions other than the size of the device. Among them, there is a method of stacking cells by a memory process using a stackable material as a stacked structure and a method of improving the information storage capacity of a device so as to store multiple information in one cell cell.

On the other hand, in the case of resistive switching memory (hereinafter referred to as ReRAM), it is advantageous to perform all the processes at a low temperature compared with the silicon process and to realize the high integration memory using the 3D lamination . However, the switching mechanism responsible for the ReRAM behavior has not yet been clarified, and research groups continue to study the principle of resistance change. It is known that the ReRAM behavior developed until now is mainly due to the movement of defects such as oxygen vacancy or silver. In order to realize low voltage operation and fast switching speed which exceed the performance of the conventional ReRAM, It is essential to develop a memory device in which the behavior is fundamentally different, that is, the movement of light ions such as hydrogen. In addition, for the practical use of ReRAM devices, it is essential to develop new materials, develop optimal deposition process technology, and secure device stability and uniformity.

The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a semiconductor memory device capable of securing a low voltage operation through stability of a resistance change memory and a fast switching speed through development of a new material and a new process technology, To a resistance change memory using hydrogen ion diffusion and a manufacturing method thereof. However, these problems are exemplary and do not limit the scope of the present invention.

According to one aspect of the present invention, a method of manufacturing a resistance change memory using hydrogen ion diffusion is provided. A method for fabricating a resistance change memory using hydrogen ion diffusion includes: forming a resistance variable layer; And a step of hydrogenating at least a part of the resistance-variable layer so as to have a property of metal-insulator transition from metal to insulator through hydrogen treatment.

A method of fabricating a resistance change memory using hydrogen ion diffusion, the method comprising: forming the resistance variable layer; And forming the first electrode layer, wherein the resistance variable layer is formed on the first electrode layer.

A method of fabricating a resistance change memory using hydrogen ion diffusion, the method comprising: forming the resistance variable layer; And then forming a second electrode layer on the resistance-variable layer.

A method of fabricating a resistance change memory using hydrogen ion diffusion, the method comprising: forming the resistance variable layer; Forming a first electrode layer on the resistance-variable layer; And forming a second electrode layer on the resistance variable layer, the second electrode layer being spaced apart from the first electrode layer.

In the method for fabricating a resistance change memory using hydrogen ion diffusion, the hydrogenation may be performed by using a mixed gas comprising an argon (Ar) component and a hydrogen (H) Ion (H & lt ; + & gt ; ).

In the method of manufacturing the resistance change memory using the hydrogen ion diffusion, the hydrogenation may use a platinum (Pt) catalyst.

In the method for fabricating a resistance change memory using hydrogen ion diffusion, the hydrogenation may be implemented by low temperature annealing using the catalyst in a temperature range of 80 ° C to 120 ° C.

In the method for fabricating a resistance change memory using hydrogen ion diffusion, the resistance variable layer may include a rare earth nickel oxide (ReNiO 3 ) having a perovskite structure.

According to another aspect of the present invention, a resistance change memory using hydrogen ion diffusion is provided. The resistance change memory using the hydrogen ion diffusion includes: a first electrode layer; A resistance variable layer formed on the first electrode layer; And a second electrode layer formed on the resistance variable layer, wherein the resistance variable layer comprises a first rare earth nickel oxide layer (ReNiO 3 ) of a metal nature and a hydrogen ion (H + ) layer formed on the first nickel oxide layer, And a second rare earth nickel oxide layer (H-ReNiO 3 ) having an insulator property added thereto, wherein a voltage is applied to the second electrode layer so that the hydrogen ions in the second rare earth nickel oxide layer are in contact with the first rare earth nickel oxide Layer, the resistance-variable layer can show characteristics of the resistance-change memory element.

According to another aspect of the present invention, a resistance change memory using hydrogen ion diffusion is provided. The resistance-change memory using hydrogen ion diffusion includes a resistance-variable layer; A first electrode layer formed on the resistance variable layer; And a second electrode layer formed on the resistance-variable layer and spaced apart from the first electrode layer, wherein the resistance-variable layer includes a first rare-earth nickel oxide layer (ReNiO 3 ) and a second electrode layer And a second rare earth nickel oxide layer (H-ReNiO 3 ) to which hydrogen ions (H + ) are added to at least a part of the first rare earth nickel oxide layer, wherein a voltage is applied to the second electrode layer to form the second rare earth nickel The hydrogen ions in the oxide layer are diffused into the first rare earth nickel oxide layer so that the resistance variable layer can show the characteristics of the resistance change memory element.

In the resistance change memory using the hydrogen ion diffusion, the first electrode layer and the second electrode layer may be arranged at the same level.

According to an embodiment of the present invention as described above, a resistance change memory using hydrogen ion diffusion with excellent interfacial characteristics and excellent information storage ability and durability by introducing a hydrogenation process method into a new material and a resistance variable layer, The manufacturing method can be implemented, and as the movement of hydrogen ions with a small weight causes a resistance change, it may cause a rapid operation of resistance change and a possibility of low voltage operation. Of course, the scope of the present invention is not limited by these effects.

1 is a diagram schematically showing a structure of a resistance change memory according to embodiments of the present invention.
2 is a schematic diagram illustrating a method of manufacturing a resistance change memory according to embodiments of the present invention.
FIG. 3 is a result of AFM analysis of the surface of the resistance variable layer sample according to the experimental example of the present invention.
FIG. 4 is a result of XRD analysis of a resistance variable layer sample according to an experimental example of the present invention.
FIG. 5 shows the results of XRD analysis of the structures of the resistance variable layer samples shown in FIG. 4 before and after hydrogenation.
FIG. 6 is a result of AFM analysis of the structure of the resistance change layer samples shown in FIG. 4 before and after the hydrogenation treatment.
FIG. 7 shows the results of analyzing resistance characteristics before and after hydrogenation of the resistance variable layer sample according to the experimental example of the present invention.
8 is a result of analyzing a resistance change memory sample according to an experimental example of the present invention by an optical microscope.
FIG. 9 is a result of analyzing the current-voltage characteristics of the resistance change memory samples shown in FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, Is provided to fully inform the user. Also, for convenience of explanation, the components may be exaggerated or reduced in size.

It is to be understood that throughout the specification, when an element such as a film, region or substrate is referred to as being "on", "connected to", "laminated" or "coupled to" another element, It is to be understood that elements may be directly "on", "connected", "laminated" or "coupled" to another element, or there may be other elements intervening therebetween. On the other hand, when one element is referred to as being "directly on", "directly connected", or "directly coupled" to another element, it is interpreted that there are no other components intervening therebetween do. Like numbers refer to like elements. As used herein, the term "and / or" includes any and all combinations of one or more of the listed items.

Although the terms first, second, etc. are used herein to describe various elements, components, regions, layers and / or portions, these members, components, regions, layers and / It is obvious that no. These terms are only used to distinguish one member, component, region, layer or section from another region, layer or section. Thus, a first member, component, region, layer or section described below may refer to a second member, component, region, layer or section without departing from the teachings of the present invention.

Also, relative terms such as "top" or "above" and "under" or "below" can be used herein to describe the relationship of certain elements to other elements as illustrated in the Figures. Relative terms are intended to include different orientations of the device in addition to those depicted in the Figures. For example, in the figures the elements are turned over so that the elements depicted as being on the top surface of the other elements are oriented on the bottom surface of the other elements. Thus, the example "top" may include both "under" and "top" directions depending on the particular orientation of the figure. If the elements are oriented in different directions (rotated 90 degrees with respect to the other direction), the relative descriptions used herein can be interpreted accordingly.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a," "an," and "the" include singular forms unless the context clearly dictates otherwise. Also, " comprise "and / or" comprising "when used herein should be interpreted as specifying the presence of stated shapes, numbers, steps, operations, elements, elements, and / And does not preclude the presence or addition of one or more other features, integers, operations, elements, elements, and / or groups.

Hereinafter, embodiments of the present invention will be described with reference to the drawings schematically showing ideal embodiments of the present invention. In the figures, for example, variations in the shape shown may be expected, depending on manufacturing techniques and / or tolerances. Accordingly, the embodiments of the present invention should not be construed as limited to the particular shapes of the regions shown herein, but should include, for example, changes in shape resulting from manufacturing.

1 is a diagram schematically showing a structure of a resistance change memory according to embodiments of the present invention.

1 (a), a resistance change memory 1000 according to an embodiment of the present invention includes a resistance change layer 200, a first electrode layer 100 formed on the resistance change layer 200, And a second electrode layer 300 formed on the resistance variable layer 200 and spaced apart from the first electrode layer 100. The first electrode layer 100 and the second electrode layer 300 may be disposed at the same level. Here, the resistance variable layer 200 is formed by partially adding the hydrogen ion (H + ) to at least a part of the resistance variable layer 200 contacting the second electrode layer 300, thereby forming a part of the resistance variable layer 200 (Metal-Insulator Transition, hereinafter referred to as MIT). Here, a part of the resistance variable layer 200 can be understood as a second rare earth nickel oxide layer 204. [

1B, the resistance change memory 1100 according to another embodiment of the present invention includes a first electrode layer 110, a resistance change layer 210 formed on the first electrode layer 110, And a second electrode layer 310 formed on the resistance-variable layer 210. Here, the resistance variable layer 210 is formed by partially adding the hydrogen ion (H + ) to at least a portion of the resistance variable layer 210 contacting the second electrode layer 310, thereby forming a part of the resistance variable layer 210 (MIT) to an insulator state. Here, a part of the resistance-variable layer 210 may be understood as a second rare earth nickel oxide layer 214. [

A detailed description of the resistance change memory 1000 or 1100 will be given later with reference to FIG. 2 to FIG. 9.

2 is a schematic diagram illustrating a method of manufacturing a resistance change memory according to embodiments of the present invention.

Referring to FIG. 2A, a method of fabricating a resistance change memory (S1000) according to an embodiment of the present invention includes forming a resistance variable layer (S100), forming a first electrode layer (S300) of forming a second electrode layer on the resistance-variable layer, the metal-insulator transition (S303) being formed on at least a part of the resistance-variable layer contacting the second electrode layer MIT) phenomenon (S400).

More specifically, referring again to FIG. 1 (a), the resistance change memory 1000 may include a resistance change layer 200 capable of performing a resistance switching behavior when a voltage is applied through an electrode. Resistance variable layer 200 is, for example, may use a number of Steel Box relationship rare earth oxides such as nickel oxide water (ReNiO 3) and rare-earth copper oxide water (ReCuO 3) (oxide correlated).

The first electrode layer 100 and the second electrode layer 300 may be formed of a metal such as nickel, copper, hafnium, tantalum, gold, , Silver (Ag), and platinum (Pt). The first electrode layer 100 and the second electrode layer 300 may be formed using any one of an electrochemical deposition method, a sputtering method, and a thermal evaporation deposition method.

The first electrode layer 100 and the second electrode layer 300 may be separately formed on the resistance variable layer 200. The first electrode layer 100 and the second electrode layer 300 may be formed on the same level When they are spaced apart from each other, they can be formed by performing a single deposition process. However, the second electrode layer 300 may be formed on at least one surface of the resistance-variable layer 200, such as a side surface of the resistance-variable layer 200, .

For example, the resistance variable layer 200 of the resistance change memory 1000 according to an embodiment of the present invention may include a first rare earth nickel oxide layer (ReNiO 3 , 202). The first electrode layer 100 and the second electrode layer 300 may be simultaneously formed on the first rare earth nickel oxide layer 202. [ The first rare earth nickel oxide layer 202 has a distorted perovskite structure. In addition, the non-covalent electrons belonging to the e g band of the first rare earth nickel oxide layer 202 have a strong correlation with each other and exhibit metal-insulator transition phenomenon depending on temperature, pressure and doping.

The first rare earth nickel oxide layer 202 has a property of being in a metal state at room temperature and is doped with a proton to the first rare earth nickel oxide layer 202 to rapidly change the physical properties from the metal state to the non- . Here, the hydrogen ion doping implies hydrogenation of at least a portion of the resistance-variable layer 202 (S400). At this time, the hydrogen ion is diffused in the resistance variable layer 202 through the voltage application, and the thickness of the insulating layer is changed to be thick, thereby realizing the hydrogen ion-based resistance variable element.

In addition, in the method of manufacturing the resistance change memory device 1000, the hydrogen ion doping method may be performed by depositing platinum Pt on the first electrode layer 100 and the second electrode layer 300, A forming gas containing an argon (Ar) component and a hydrogen (H) component is supplied onto the silicon substrate 202 and annealed at a temperature ranging from about 80 ° C to 120 ° C to form a rare earth nickel oxide (ReNiO 3 ) may be added to at least a part of the hydrogen ions (H + ). At this time, the second electrode layer 300 acts as a catalyst, and dissociates the hydrogen gas molecules contained in the mixed gas. The second rare earth nickel oxide layer (H-ReNiO 3 , 204) to which hydrogen ions (H + ) are added is formed around the second electrode layer 300 by the hydrogenation process, thereby controlling the band gap.

On the other hand, the first rare earth nickel oxide layer 202 has a small band gap near the Fermi level and causes charge unevenness. Here, at least a part of the first rare earth nickel oxide layer 202 is hydrogenated to compensate electrons to nickel ions (Ni 4+ ), thereby adjusting the bandgap of the first rare earth nickel oxide layer 202 . In addition, the perovskite crystal structure of the first rare earth nickel oxide layer 202 can be reversibly maintained by the hydrogenation process and the annealing process in an ozone (O 3 ) atmosphere.

Therefore, the platinum of the second electrode layer 300 facilitates the addition of hydrogen ions in the first rare earth nickel oxide layer (ReNiO 3 , 202) as a catalyst, and the second rare earth nickel oxide layer (H-ReNiO 3 , 204), when the first electrode layer 100 is grounded and the voltage V G is applied to the second electrode layer 300, As the area of the insulator to which hydrogen is added increases according to the voltage using the insulation transition characteristics, the function as the nonvolatile resistance change memory device 1000 can be performed.

Referring to FIG. 2B, a method of fabricating a resistance-variable memory S1100 according to another embodiment of the present invention includes forming a first electrode layer S110, forming a resistance-variable layer on the first electrode layer, Forming a second electrode layer on the resistance-variable layer (S310); and performing a hydrogenation process (S410) so as to have a metal-insulator transition property on at least a part of the resistance-variable layer.

More specifically, referring back to FIG. 1B, the resistance change memory 1100 may form the resistance variable layer 210 on the first electrode layer 110. The resistance change memory 1100 can be manufactured by forming the second electrode layer 310 on the resistance change layer 210 and then hydrogenating at least a portion of the resistance change layer 210. [ Here, the materials and the forming method of the first electrode layer 110 and the second electrode layer 310 are the same as those described above with reference to FIGS. 1A and 2 (A), and therefore will not be described. The hydrogenation treatment will be omitted since it is the same as that described above with reference to Figs. 1 (a) and 2 (a).

The resistance change memory 1100 uses platinum Pt as the first electrode layer 110 and a first rare earth nickel oxide layer ReNiO 3 212 as a resistance change layer on the first electrode layer 110. [ As shown in FIG. Thereafter, a second rare earth nickel oxide layer 212 is formed on the first rare earth nickel oxide layer 212 by using platinum Pt as the second electrode layer 310 on the first rare earth nickel oxide layer 212, layer can form a (H-ReNiO 3, 214) .

In addition, the platinum of the second electrode layer 310 facilitates the addition of hydrogen ions in the first rare earth nickel oxide layer (ReNiO 3 , 212) as a catalyst, and the second rare earth nickel oxide In the device including the layer (H-ReNiO 3 , 214), when the first electrode layer 110 is grounded and the voltage V G is applied to the second electrode layer 310, - It can perform its function as a nonvolatile resistance-change memory device by using an insulating transition phenomenon.

The resistance change memory 1000 shown in FIG. 1A can form the first electrode layer 100 and the second electrode layer 300 at the same time. Therefore, the resistance change memory 1000 shown in FIG. The manufacturing process becomes simpler than the manufacturing process 1100, so that the process time can be shortened and the economical effect can be obtained.

Meanwhile, the second rare earth nickel oxide layer 214 may be directly deposited on the first rare earth nickel oxide layer 212 without a platinum catalyst. That is, before the second electrode layer 310 is formed on the first rare earth nickel oxide layer 212, a metal oxide (e.g., a metal oxide) is formed using a chemical vapor deposition method such as electrochemical deposition or chemical vapor deposition Layer may be formed. In this case, there is no need for a separate hydrotreatment step, so that the process can be simplified.

Hereinafter, an experimental example to which the technical idea described above is applied will be described in order to facilitate understanding of the present invention. It should be understood, however, that the following examples are for the purpose of promoting understanding of the present invention and are not intended to limit the scope of the present invention.

A LaAlO 3 substrate and an LSAT (La 0.3 Sr 0.7 Al 0.65 Ta 0.35 O 3 ) substrate were prepared. NdNiO 3 was grown on the two substrates to a thickness of about 25 nm using a pulse laser deposition method. A Pt (Pt) electrode array was formed on the NdNiO 3 by a distance of about 50 탆. Thereafter, a mixed gas containing about 5% of hydrogen (H2) and about 95% of argon (Ar) was supplied to the NdNiO 3 phase at a flow rate of about 0.5 LPM and annealed at about 100 ° C for about 1 hour At least a part of NdNiO 3 was doped with a hydrogen ion to prepare a resistance change layer sample exhibiting metal-heat transfer transition characteristics.

FIG. 3 shows the result of AFM analysis of the surface of the resistance variable layer sample according to the experimental example of the present invention, and FIG. 4 shows the result of XRD analysis of the resistance variable layer sample according to the experimental example of the present invention.

Referring to FIG. 3, the result of analyzing the surface of the resistance variable layer sample with an atomic force microscope (AFM). 3 (a), the surface of the LaAlO 3 substrate was measured with an AFM. As a result, it can be seen that the surface of the LaAlO 3 substrate was grown with a (100) orientation. The root-mean-square (RMS) value of the portion of the substrate surface of the resistance-change memory sample denoted by P1 was 0.143 nm.

Further, according to FIG. 3 (b), the surface of the sample having NdNiO 3 formed on the LaAlO 3 substrate was measured with an AFM, and it was found that the sample was grown with the same (100) plane as the orientation of the substrate . The RMS value of the portion indicated by P2 in the surface of the resistance variable layer sample was 0.162 nm. Therefore, the results can be seen that the 3 and NdNiO well grown on the substrate along the surface of the LaAlO 3 substrate.

Referring to FIG. 4, the structure of the resistance variable layer sample is analyzed by XRD. According to the sample 3 of about NdNiO 25㎚ thickness formed on the sample is about 25㎚ NdNiO 3 is formed with a thickness of the LSAT substrate on a LaAlO 3 substrate was analyzed by XRD, respectively, the diffraction peak angle depends on the components of the substrate And the diffraction peak of NdNiO 3 is shifted. However, it can be confirmed that the diffraction peak of the NdNiO 3 is well formed with the (100) plane which is the same as the orientation of each substrate.

FIG. 5 shows the result of XRD analysis of the structure of the resistance variable layer shown in FIG. 4 before and after hydrogenation, FIG. 6 shows the structure of the resistance variable layer samples before and after the hydrogenation treatment shown in FIG. This is a result.

Referring to FIG. 5, the structure of the resistance variable layer samples shown in FIG. 4 before / after the hydrogenation treatment is analyzed by XRD. 5 (a), 5 (c) and 5 (e) show the results of XRD analysis at 150 ° C., 200 ° C. and 250 ° C., respectively, of the samples having NdNiO 3 formed on the LaAlO 3 substrate, ), (d) and (f) are the results of XRD analysis at 150 ° C, 200 ° C and 250 ° C, respectively, of the hydrogenation temperatures of samples in which NdNiO 3 was formed on the LSAT substrate.

In both cases, it can be seen that as the hydrotreating temperature increases, the diffraction peak shifts to the left. Also, it can be confirmed that the diffraction peak of the metal oxide layer is abruptly shifted to the left from 150 ° C to 200 ° C based on the temperature of 200 ° C, and no large shift change is observed at 200 ° C or more.

6 (a) and 6 (c) are graphs showing the results of analysis of the surface before and after the hydrogenation treatment of the sample in which NdNiO 3 was formed on the LaAlO 3 substrate, and it was confirmed that the RMS value was 0.115 nm after the hydrogenation treatment at 0.144 nm . 6 (b) and 6 (d) are results of analysis of the surface before and after the hydrogenation treatment of the sample on which NdNiO 3 was formed on the LSAT substrate, and it was confirmed that the RMS value was 0.169 nm after hydrogenation treatment at 0.148 nm have. Both results show that NdNiO 3 is uniformly formed on the entire surface of the sample.

FIG. 7 shows the results of analyzing resistance characteristics before and after hydrogenation of the resistance variable layer sample according to the experimental example of the present invention.

First, referring to FIG. 7A, a microscope analysis of an array of platinum (Pt) electrodes 300 spaced apart from one another by a length of about 50 μm on the resistance-variable layer of the resistance- , It can be confirmed that the platinum electrodes are arranged in parallel at regular intervals.

According to (b) of Figure 7, as a result of measuring the specific resistance of the hydrogenation temperature of the respective sample, the sample is NdNiO 3 formed on the sample and the LSAT substrate is NdNiO 3 formed on a LaAlO 3 substrate if the heat treatment without platinum It can be seen that there is no change in resistivity depending on the heat treatment temperature.

On the other hand, it can be confirmed that the resistivity value after the hydrogenation treatment is higher than the resistivity value before the hydrogenation treatment in both of the samples having the platinum catalyst electrode. It can be confirmed that the resistivity value is increased by about 10 5 or more as the hydrogenation temperature increases in all cases except for the sample in which NdNiO 3 is formed on the LaAlO 3 substrate subjected to hydrogenation at 150 ° C. It can also be seen that the resistivity values of the two samples are similarly measured at the hydrogenation temperature of about 200 ° C or higher.

FIG. 8 is a result of analyzing the resistance change memory sample according to the experimental example of the present invention by an optical microscope, and FIG. 9 is a result of analyzing the current-voltage characteristics of the resistance change memory samples shown in FIG.

Referring to FIG. 8, the resistance-change memory sample shows that the small-sized platinum electrode 300 injects hydrogen ions, while the large-sized platinum electrode 100 does not inject hydrogen ions, . As a result, hydrogen ions are implanted into the NdNiO 3 region around the platinum electrode 300 having a small size.

9, when either one of the platinum electrodes of the resistance-change memory sample is grounded and a bias is applied to the other of the platinum electrodes, the area of the electrode (the platinum electrode 300 shown in FIG. 8) The narrower the samples are, the more typical bipolar resistance change behavior is observed.

A DC sweeping voltage of 0 V? 5 V? 0 V? -5 V? 0 V is sequentially applied to the hydrogenated platinum electrode and the other electrode not subjected to the hydrogen treatment is grounded, Both the Low Resistive State and the High Resistive State are observed in the current-voltage results.

Also, during the first sweep (when a positive bias is applied), the volume of the rare earth nickel oxide layer (H-ReNiO 3 ) having hydrogen ions of an insulator property at the interface of the electrode is set to about 5 V from the set voltage 0 . As a result, the resistance variable layer NdNiO 3 is assumed to be in a high resistance state.

On the other hand, when a voltage of opposite polarity (when a negative bias is applied) is applied to the platinum electrode, hydrogen ions gather near the interface to increase the volume of the rare-earth nickel oxide layer (ReNiO 3 ) It is switched to the resistance state.

Further, a DC sweeping voltage of 0 V? 10 V? 0 V? -10 V? 0 V is sequentially applied to the platinum electrode and the other electrode is grounded, and the current-voltage result of the resistance- Both the Low Resistive State and the High Resistive State are observed. Since a resistance in a low resistance state and a resistance state in a high resistance state are changed according to an applied voltage, a multi-level resistance switching element can be realized by using a device of the proposed structure.

As described above, the rare earth nickel oxide-based resistance-change element is a resistance-change memory element capable of causing a resistance change due to the movement of hydrogen ions. Until now, most resistance memory devices have been driven by oxygen vacancies, but the implementation of resistance memory devices with hydrogen ions has not been reported yet. Through this, a multi-level resistance change memory having a small operating voltage and a fast switching speed can be realized. Further, the resistance variable memory element has a disadvantage in that the driving voltage and the current greatly change in each operation. This is because some of the insulator (or metal) regions created in the device are not individually uniformly controlled.

In order to solve this problem, the present invention can provide a hydrogen ion-based resistance change memory element by hydrogenating the rare earth nickel oxide resistance variable layer. In addition, the present invention can provide a new material capable of overcoming the size limitation of a resistance change memory element used as a nano device, and a resistance change memory implemented by a new method.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

100, 110: first electrode layer
200, 210: resistance variable layer
202, 212: first rare earth nickel oxide layer
204, 214: a second rare earth nickel oxide layer
300, 310: second electrode layer
1000, 1100: Resistance change memory

Claims (11)

Forming a first electrode layer;
Forming a resistance variable layer having a perovskite structure on the first electrode layer;
Forming a second electrode layer on the resistance-variable layer; And
A step of hydrogenating at least a part of the resistance-variable layer so as to have a property of metal-insulator transition from metal to insulator through hydrogen treatment;
Lt; / RTI >
(H + ) is added to at least a part of the resistance-variable layer by using the second electrode layer formed on the resistance-variable layer as a catalyst so that at least a part of the resistance-variable layer has an insulator property, Lt; / RTI >
A method of fabricating a resistance change memory using hydrogen ion diffusion. delete delete delete The method according to claim 1,
The hydrogenation is performed by adding the hydrogen ion (H + ) to at least a part of the resistance variable layer using a forming gas comprising an argon (Ar) component and a hydrogen (H) A method of fabricating a resistance change memory using the method. The method according to claim 1,
Wherein the second electrode layer comprises a platinum (Pt) catalyst,
The hydrogenation may be performed by using a platinum (Pt) catalyst to dope the hydrogen ions in the vicinity of the resistance-variable layer and the catalyst,
A method of fabricating a resistance change memory using hydrogen ion diffusion. The method according to claim 6,
Wherein the hydrogenation is performed by annealing the catalyst at a temperature ranging from 80 DEG C to 120 DEG C,
A method of fabricating a resistance change memory using hydrogen ion diffusion. The method according to claim 1,
Wherein the resistance variable layer comprises rare earth nickel oxide (ReNiO 3 )
And at least a part of the rare earth nickel oxide is doped by the hydrogenation to form an insulator property,
A method of fabricating a resistance change memory using hydrogen ion diffusion. A first electrode layer;
A resistance variable layer formed on the first electrode layer; And
A second electrode layer formed on the resistance-variable layer;
/ RTI >
The resistance-variable layer may be formed by doping hydrogen ions (H + ) on the first rare earth nickel oxide layer using a metal first rare earth nickel oxide layer (ReNiO 3 ) and the second electrode layer as a catalyst, A second rare earth nickel oxide layer (H-ReNiO 3 )
And a resistance variable layer is formed on the resistance variable layer by applying a voltage to the second electrode layer to diffuse the hydrogen ions in the second rare earth nickel oxide layer into the first rare earth nickel oxide layer,
Resistance change memory using hydrogen ion diffusion. A resistance variable layer;
A first electrode layer formed on the resistance variable layer; And
A second electrode layer formed on the resistance-variable layer and spaced apart from the first electrode layer;
/ RTI >
The resistance variable layer may be formed by doping a hydrogen ion (H + ) in the vicinity of the first rare earth nickel oxide layer (ReNiO 3 ) and the second electrode layer as a catalyst, A second rare earth nickel oxide layer (H-ReNiO 3 ) having an insulator property,
And a resistance variable layer is formed on the resistance variable layer by applying a voltage to the second electrode layer to diffuse the hydrogen ions in the second rare earth nickel oxide layer into the first rare earth nickel oxide layer,
Resistance change memory using hydrogen ion diffusion. 11. The method of claim 10,
Wherein the first electrode layer and the second electrode layer are disposed at the same level,
Resistance change memory using hydrogen ion diffusion.
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JP2014063877A (en) 2012-09-21 2014-04-10 Fujitsu Ltd Resistance variable memory and driving method thereof

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