JP5120967B2 - Variable resistance element - Google Patents

Description

  The present invention relates to a variable resistance element in which an electric resistance is reversibly changed by changing a voltage applied to a metal oxide sandwiched between two electrodes, a manufacturing method thereof, and the variable resistance element The present invention relates to a non-volatile memory device having a memory cell as a memory cell.

  In recent years, the increase in capacity of nonvolatile semiconductor memory devices represented by flash memory has been remarkable, and products having a capacity of about 4 GB at the product level are sold at a price of about tens of thousands of yen. In particular, as a portable or portable memory such as a USB memory, the value of the product is increasing, and the market has been losing the market that has been occupied by magneto-optical disks and the like.

  In addition, the capacity of several gigabytes is sufficient as storage for portable music players, and portable music with a non-volatile semiconductor memory device that is a solid-state device separate from the hard disk-equipped portable music players that are rapidly spreading. Players have succeeded in appealing to users the fundamental advantages of solid-state memory such as vibration resistance, high reliability, and low power consumption. Furthermore, it is expected to become mainstream as a portable or portable commodity storage for music and images.

  In the future, if further increase in capacity and reduction in bit cost are realized, the nonvolatile semiconductor memory device is expected to be a portable or portable product storage for recording and reproducing moving images. Further research is underway.

In particular, the nonvolatile semiconductor memory device has the following limitations due to the operation principle of the flash memory while taking over the low cost and small cell area (˜4F ² : F is the minimum processing dimension of the manufacturing process), which are the advantages of the flash memory. If (1) high write / erase voltage (requires a booster circuit), (2) slow write / erase operation (especially erase time is over 100 μsec), (3) small number of rewrites (less than 10 ⁶ times) can be overcome. Applications for replacing DRAMs used as the main memory of current information equipment will be developed. This makes it possible to realize a so-called “instant-on computer” that is instantly activated during use and consumes as much power as possible during standby.

  As candidates for such next-generation non-volatile semiconductor memory devices, research and development of non-volatile memory elements based on their own principles such as ferroelectric memory (FeRAM), magnetic memory (MRAM), etc. have been conducted. It is difficult to surpass the low bit cost and small cell area that are the features of memory.

  Under such circumstances, phase change memory (PRAM), resistance change type memory (RRAM: registered trademark), and the like are attracting attention because they may surpass the bit cost of flash memory. The resistance change type memory mentioned here includes a variable resistance element composed of two electrodes and a metal oxide sandwiched between the two electrodes as a data storage unit. By applying a voltage (or current) that is equal to or higher than the threshold voltage (or threshold current) to the electrode, the electric resistance of the variable resistance element can be changed, and even after the voltage (or current) application state has been canceled once The resistance state is maintained in a nonvolatile manner. Thereby, the resistance change type memory can store information corresponding to different resistance states in the variable resistance element.

  For example, the following Patent Document 1 and Non-Patent Document 1 disclose “a method of changing a resistance value by applying voltage pulses of different polarities to a thin film made of a perovskite material sandwiched between a pair of electrodes”. Yes. However, this perovskite substance has a problem in terms of affinity with a general semiconductor process.

As a solution to this problem, Patent Document 2 discloses a resistance change type memory made of a binary oxide having a high affinity with a semiconductor process and having a simple composition. Specifically, Patent Document 2 states that “the data storage material layer has different resistance characteristics at different voltages and NiO, V ₂ O ₅ as transition metal oxide films whose resistance rapidly increases in a predetermined voltage range. , ZnO, Nb ₂ O ₅ , TiO ₂ , WO ₃ or CoO ”is disclosed.

Non-Patent Document 2 includes an upper electrode and a lower electrode, and NiO, TiO ₂ , ZrO ₂ , or HfO ₂ that is a binary transition metal oxide sandwiched between the two electrodes. An example of a nonvolatile resistance change memory element has been reported.

  As described above, the resistance change type memory made of a binary transition metal oxide disclosed in Patent Document 2 or Non-Patent Document 2 has a high affinity with a semiconductor process and has a simple structure and composition. There is an advantage that it can be easily applied to a highly integrated nonvolatile memory.

US Pat. No. 6,204,139 (published March 20, 2001) JP 2004-363604 A (published on December 24, 2004)

“Electric-pulse-induced reversible resistance change effect in magneto-sensitive films” Applied Physics Letter, Vol. 76, pp. 2749-2751, 2000 "Highly Scalable Non-volatile Resistive Memory Using Simple Binary Oxide Driven by Asymmetric Unipolar Voltage Pulses," IEDM Tech. 587-590, 2004

  However, in a resistance change type memory made of a binary transition metal oxide disclosed in Patent Document 2 or Non-Patent Document 2, a soft breakdown called forming is included in a variable resistance element constituting the resistance change type memory. It is necessary to perform an initialization process that causes Specifically, the forming is to form a conduction path in the metal oxide that conducts between the two electrodes by applying a predetermined potential difference between the two electrodes. Here, when considering application to a highly integrated nonvolatile memory, it is very important to reduce the voltage required for forming (hereinafter referred to as forming voltage) from the viewpoint of simplification of peripheral circuits.

  Here, it is known that this forming voltage is substantially proportional to the film thickness of the metal oxide sandwiched between the electrodes. By reducing this film thickness, the forming voltage can be reduced. Conceivable. However, if the film thickness is reduced to such an extent that a forming voltage of several volts or less is realized, there arises a problem that leakage current increases as the film thickness is reduced.

  The present invention has been made to solve the above-described problem, and its purpose is to provide a variable resistance element capable of reducing a forming voltage for forming a conducting portion in a metal oxide without increasing a leakage current, An object of the present invention is to provide a manufacturing method thereof and a nonvolatile memory device including the variable resistance element as a memory layer.

In order to solve the above problems, the variable resistance element of the present invention is
A first electrode and a second electrode; and a metal oxide sandwiched between the first electrode and the second electrode, the first electrode depending on a voltage applied between the first electrode and the second electrode. A variable resistance element in which electrical resistance between an electrode and the second electrode reversibly changes, wherein the metal oxide is separated from at least one of the first electrode and the second electrode in the metal oxide. Further, it is characterized by further including a low resistance material having a lower electrical resistance than the above.

  First, in the variable resistance element, the electrical resistance between the first electrode and the second electrode is reversibly changed according to the voltage applied to the first and second electrodes, in other words, in the low resistance state and the high resistance state. In order to change to either one, it is necessary to perform an initialization process called forming in advance on the variable resistance element. Specifically, in this forming, a predetermined voltage (hereinafter referred to as a forming voltage) is applied between two electrodes to form a conduction path in the metal oxide that conducts between the two electrodes. It is. The magnitude of this forming voltage is proportional to the thickness of the metal oxide that needs to form a conduction path.

  Here, in order to realize a reduction in the forming voltage, the variable resistance element of the present invention includes a low resistance material having an electric resistance lower than that of the metal oxide in the metal oxide. Thereby, the conductive path formed by forming does not need to connect between the first electrode and the second electrode, and the electrode (the first electrode and the second electrode is separated from the low resistance material from the low resistance material). It may be formed so as to connect up to at least one).

  In other words, in the case of a variable resistance element that does not have a low resistance in the metal oxide as in the prior art, the thickness of the metal oxide that needs to form a conduction path is the same as that of the first electrode and the second electrode. This is the distance to the electrode. In contrast, in the variable low-resistance element of the present invention, the thickness of the metal oxide that needs to form a conduction path corresponding to the provision of the low-resistance material in the metal oxide has the first electrode and the second electrode. Less than the distance. As a result, the variable resistance element of the present invention can reduce the forming voltage.

  In the variable resistance element of the present invention, the forming voltage can be lowered without reducing the thickness of the metal oxide sandwiched between the first electrode and the second electrode. This suppresses an increase in leakage current caused by reducing the thickness of the metal oxide.

  As described above, the variable resistance element of the present invention has an effect that the forming voltage for forming the conductive portion in the metal oxide can be reduced without increasing the leakage current.

The variable resistance element according to the present invention further includes
The low resistance material is preferably composed of at least one of an element constituting the first electrode and an element constituting the second electrode.

  With the above configuration, the low resistance can be generated by processing the first electrode or the second electrode, and the variable resistance element can be easily manufactured.

The variable resistance element according to the present invention further includes
The low resistance material is preferably composed of at least one kind of metal element constituting the metal oxide.

  With the above configuration, the low resistance can be generated by processing the metal oxide, and the variable resistance element can be easily manufactured.

The variable resistance element according to the present invention further includes
The metal oxide is polycrystalline, and the low resistance material is preferably formed at a grain boundary of the metal oxide.

  With the above configuration, the low resistance can be easily formed at the grain boundary of the metal oxide by utilizing the grain boundary diffusion. In addition, since the variable resistance element of the present invention can localize the low-resistance material by providing the above-described configuration, the portion where the thickness of the metal oxide is locally thinned by the presence of the low-resistance material is reduced. As a result, the leakage current can be kept low.

The variable resistance element according to the present invention further includes
The low resistance material is preferably formed by diffusing an element constituting at least one of the first electrode or the second electrode into the metal oxide by heat treatment.

  According to the above configuration, the element constituting at least one of the first electrode or the second electrode diffuses into the metal oxide by the heat treatment. Here, since the diffused element is an element constituting at least one of the first electrode and the second electrode, it has conductivity. That is, this conductive element diffuses into the metal oxide, thereby forming a low-resistance material in the metal oxide. In addition, since this element is diffused into the metal oxide using heat treatment, the diffused element takes oxygen from the metal oxide and reduces it, thereby forming the metal oxide in the metal oxide. It is also possible to form a metal element as a low resistance material.

  As described above, the provision of the above configuration has an effect that a low resistance material can be reliably formed in the metal oxide.

In order to solve the above problems, the variable resistance element of the present invention is
A first electrode and a second electrode; and a metal oxide sandwiched between the first electrode and the second electrode, the first electrode depending on a voltage applied between the first electrode and the second electrode. A variable resistance element in which an electrical resistance between the electrode and the second electrode reversibly changes, and the metal oxide is sequentially disposed between at least one of the first electrode and the second electrode and the metal oxide. A first region composed of a first metal element constituting the metal oxide and oxygen, wherein the ratio of the number of oxygen atoms to the number of atoms of the first metal element is high; and the first region And a second region composed of at least one of the first electrode and the second electrode, the first metal element, and oxygen. It is characterized by being.

  With the above configuration, the variable resistance element of the present invention has an effect that the forming voltage for forming the conductive portion in the metal oxide can be reduced without increasing the leakage current.

The variable resistance element according to the present invention further includes
The second metal element is preferably aluminum.

The variable resistance element according to the present invention further includes
The metal oxide is preferably nickel oxide.

In order to solve the above problems, the variable resistance element manufacturing method of the present invention provides:
A first electrode and a second electrode; and a metal oxide sandwiched between the first electrode and the second electrode, the first electrode depending on a voltage applied between the first electrode and the second electrode. A variable resistance element manufacturing method in which resistance between an electrode and the second electrode reversibly changes, and diffusion for diffusing an element constituting at least one of the first electrode or the second electrode into the metal oxide And a low-resistance material having a lower electrical resistance than the metal oxide, separated from at least one of the first electrode and the second electrode in the metal oxide by the element diffused in the diffusion step And a forming step for forming the structure.

  With the above-described configuration, the variable resistance element manufacturing method of the present invention manufactures a variable resistance element that can reduce the forming voltage for forming a conducting portion in the metal oxide without increasing the leakage current. be able to.

  Furthermore, according to the method of manufacturing a variable resistance element described above, a complicated process is not required in which a void is intentionally formed in the metal oxide and a low resistance material is embedded therein. As a result, the variable resistance element can be easily and inexpensively manufactured.

The variable resistance element manufacturing method according to the present invention further includes:
It is preferable to perform the said diffusion process by heat processing.

  With the above configuration, it is possible to form a low-resistance material in the metal oxide only by heat treatment, and as a result, it is possible to produce a variable resistance element more easily and inexpensively.

In addition, the nonvolatile semiconductor memory device according to the present invention includes:
A memory cell having the variable resistance element according to any one of claims 1 to 5 and a voltage corresponding to information input from the outside are applied to the first electrode and the second electrode, and the variable A data writing means for writing the information to the memory cell by changing an electric resistance of the resistance element, a predetermined voltage applied to the first electrode and the second electrode, and a current value flowing through the variable resistance element And an information reading means for reading out information stored in the memory cell from the detected current value.

  According to the above configuration, the nonvolatile semiconductor memory device of the present invention includes the variable resistance element of the present invention as a memory cell. Therefore, since the forming voltage at the time of forming can be reduced without increasing the leakage current, the power consumption during forming can be reduced. Furthermore, since the forming voltage can be lowered, it is not necessary to make the electronic components that constitute the circuit for applying a voltage to the variable resistance element have a high withstand voltage specification, and as a result, the cost can be reduced.

  As described above, the variable resistance element of the present invention includes the first electrode and the second electrode, and the metal oxide sandwiched between the first electrode and the second electrode, and includes the first electrode and the first electrode. A variable resistance element in which an electrical resistance between the first electrode and the second electrode reversibly changes according to a voltage applied to two electrodes, wherein the first electrode and the second electrode are included in the metal oxide. Further provided is a low-resistance material having a lower electrical resistance than the metal oxide and spaced from at least one of the electrodes.

  In addition, as described above, the variable resistance element of the present invention includes the first electrode and the second electrode, and the metal oxide sandwiched between the first electrode and the second electrode. A variable resistance element in which an electrical resistance between the first electrode and the second electrode reversibly changes according to a voltage applied between the second electrodes, and at least one of the first electrode and the second electrode The number of oxygen atoms with respect to the number of atoms of the first metal element, which is composed of the first metal element and oxygen constituting the metal oxide in order from the metal oxide side between the metal oxide and the metal oxide. A first region having a high ratio, a second metal element adjacent to the first region and constituting at least one of the first electrode and the second electrode, the first metal element, and oxygen And a second region composed of:

  In addition, as described above, the variable resistance element manufacturing method of the present invention includes the first electrode and the second electrode, and the metal oxide sandwiched between the first electrode and the second electrode. A variable resistance element manufacturing method in which a resistance between the first electrode and the second electrode reversibly changes in accordance with a voltage applied between one electrode and the second electrode, wherein the first electrode or the second electrode A diffusion step of diffusing an element constituting at least one of the electrodes into the metal oxide; and at least one of the first electrode and the second electrode in the metal oxide by the element diffused in the diffusion step. Forming a low resistance object having a lower electrical resistance than the metal oxide, separated from one side.

  Therefore, the variable resistance element and the manufacturing method thereof according to the present invention can reduce the forming voltage for forming the conductive portion in the metal oxide without increasing the leakage current.

It is sectional drawing which shows the structure of the variable resistance element before forming based on one Embodiment of this invention. (A) And (b) is sectional drawing which shows the structure of the variable resistance element after forming based on one Embodiment of this invention. It is sectional drawing which shows the structure of the variable resistance element before forming which comprises a non-contact low-resistance thing in two electrodes based on one Embodiment of this invention. (A) And (b) is sectional drawing which shows the structure of the variable resistive element after forming with respect to the variable resistive element of FIG. 3 based on one Embodiment of this invention. (A)-(e) is sectional drawing which shows the structure for every manufacturing process of the variable resistance element in the manufacture stage based on one Embodiment of this invention. It is a graph which shows the current-voltage characteristic at the time of forming of the variable resistance element which heat-processed and the variable resistance element which did not heat-process based on one Embodiment of this invention. It is a graph which shows the current-voltage characteristic of a variable resistance element at the time of applying the positive polarity forming voltage and set voltage and negative polarity reset voltage which concern on one Embodiment of this invention to a variable resistance element. It is a graph which shows the read-out electric current value which flows into a variable resistance element for every switching operation based on one Embodiment of this invention. It is a graph which shows the current-voltage characteristic of a variable resistance element when the positive forming voltage, the set voltage, and the reset voltage which concern on one Embodiment of this invention are applied to a variable resistance element. It is a graph which shows the read-out electric current value which flows into a variable resistance element for every switching operation based on one Embodiment of this invention. (A) is drawing which shows the TEM image of the cross section of the variable resistance element in a prior art example, (b) is drawing which shows the TEM image of the cross section of the variable resistance element based on one Embodiment of this invention. . (A) is a graph which shows the element distribution of the cross section of the variable resistance element in a prior art example, (b) is a graph which shows the element distribution of the cross section of the variable resistance element based on one Embodiment of this invention. . It is a block diagram which shows the structure of the non-volatile semiconductor memory device based on other embodiment of this invention. It is a schematic diagram which shows the structure of the memory cell array with which the non-volatile semiconductor memory device which concerns on other embodiment of this invention is provided. It is sectional drawing which shows the structure of the variable resistance element in a prior art example.

  Before describing the variable resistance element according to the present embodiment and the method of manufacturing the variable resistance element, first, a variable resistance element according to the related art will be described as a reference example with reference to FIG.

[Reference example]
FIG. 15 is a cross-sectional view showing the configuration of the variable resistance element 3 before forming in the prior art. A detailed description of forming will be given later. As shown in FIG. 15, the variable resistance element 3 includes electrodes 11 and 12 and a metal oxide layer 10 made of a metal oxide sandwiched between the electrodes 11 and 12.

  Here, the target operation of the variable resistance element 3 will be briefly described. The intended operation of the variable resistance element 3 is that the electrical resistance between the electrode 11 and the electrode 12 changes according to the threshold voltage applied to the electrodes 11 and 12. Specifically, according to the value of the threshold voltage to be applied, the electrical resistance between the electrode 11 and the electrode 12 is either a low resistance state or a high resistance state.

  In the following description, for the sake of convenience of explanation, the low resistance operation in which the electrical resistance between the electrode 11 and the electrode 12 in the variable resistance element 3 transitions from the high resistance state to the low resistance state is referred to as a set operation. The high resistance operation that transitions from the resistance state to the high resistance state is referred to as a reset operation. Further, the set operation and the reset operation are collectively referred to as a switching operation.

(Forming)
Here, in order for the variable resistance element 3 to perform the switching operation as described above, a soft breakdown is caused in the metal oxide layer 10, which is called forming, in advance with respect to the variable resistance element 3 shown in FIG. 15. Initialization processing is required. Specifically, it is necessary to form a filament as a local conductive path in the metal oxide layer 10 by applying a predetermined voltage (hereinafter referred to as a forming voltage) between the electrodes 11 and 12. There is.

  Thus, the variable resistance element 3 can perform a switching operation only after forming a filament in the metal oxide layer 10 by forming. Regarding the operation mechanism in the switching operation of the variable resistance element 3, the breakage and conduction of the filament in the metal oxide layer 10 are switched according to the threshold voltage applied to the electrodes 11 and 12, whereby the variable resistance element 3 is switched. Is considered to switch to a low resistance state or a high resistance state.

  Here, the forming voltage when forming the variable resistance element 3 is determined by the film thickness of the metal oxide layer 10. That is, as the film thickness increases, a higher forming voltage needs to be applied. Therefore, it is possible to reduce the forming voltage by reducing the film thickness, but the leakage current increases by making the metal oxide layer 10 thinner.

(Problems caused by leakage current)
Next, problems caused by the increase in leakage current will be described. First, the variable resistance element 3 is used for a memory cell in a nonvolatile memory device. Specifically, the electric resistance of the variable resistance element 3 can be switched to one of the low resistance state and the high resistance state described above according to the information to be stored (bit value or the like). When reading stored information from the nonvolatile memory device, a voltage for reading information (hereinafter referred to as a read voltage) is applied to the variable resistance element 3 in accordance with the low resistance state or the high resistance state. By detecting the current, the stored information is read out. Here, the portion responsible for the change in resistance value between the low resistance state and the high resistance state of the variable resistance element 3 (hereinafter referred to as resistance change) is a very small part where the filament in the metal oxide layer 10 is formed. It is limited to. Therefore, the metal oxide other than the portion where the filament is formed has no function. The intrinsic resistance change ratio (ratio of the resistance value in the low resistance state to the resistance value in the high resistance state) is determined by the resistance value at the time of conduction and the resistance value at breakage of only the filament portion, but a read voltage is applied to the electrodes 11 and 12. If so, current flows also in the metal oxide other than the filament portion. For this reason, this current becomes a dominant component of the current in the high resistance state, which may reduce the apparent resistance change ratio. That is, in the variable resistance element 3 of the prior art, when the metal oxide layer 10 is thinned to reduce the forming voltage, the leakage current increases, and this increased leakage current is the main component of the current in the high resistance state. Thus, there arises a problem that the resistance change ratio of the variable resistance element 3 is lowered. In general, in a metal oxide that exhibits non-linear current-voltage characteristics, for example, when the film thickness of the metal oxide layer 10 is halved, the current when the same read voltage is applied increases more than twice.

[First Embodiment]
The variable resistance element 1 according to the present invention solves the problems of the variable resistance element 3 according to the related art as described above, and specifically, forming at the time of forming without increasing the leakage current. The voltage can be lowered.

  The variable resistance element 1 according to the first embodiment of the present invention will be described below with reference to FIGS.

(Configuration of variable resistance element 1)
FIG. 1 is a cross-sectional view showing the configuration of the variable resistance element 1 according to the first embodiment. As shown in FIG. 1, the variable resistance element 1 includes electrodes 11 and 12 and a metal oxide layer 10 made of a metal oxide sandwiched between the electrodes 11 and 12. Furthermore, the variable resistance element 1 includes a low resistance material 14 having a lower electrical resistance than the metal oxide in the metal oxide layer 10. 1 is in contact with the electrode 11 and is not in contact with the electrode 12. The variable resistance element 1 shown in FIG. In FIG. 1, the distance from the electrode 11 to the electrode 12, in other words, the film thickness of the metal oxide layer 10 is the distance d0, and the distance from the low resistance 14 to the electrode 12 is the distance d1.

  Here, as shown in FIG. 1, when the low resistance 14 is locally provided in the metal oxide layer 10, the film thickness that determines the forming voltage at the time of forming is the distance d1 in FIG. That is, a voltage value corresponding to the distance d0 between the electrode 11 and the electrode 12 is required as the forming voltage when the low-resistance material 14 is not provided. Can be reduced. Further, in this case, since the distance d0 can be increased or the distance d0 does not need to be decreased in order to suppress the leakage current flowing in the metal oxide layer 10 other than the filament portion, the resistance change of the variable resistance element 1 can be reduced. A decrease in the ratio can be suppressed.

  As described above, the variable resistance element 1 according to the first exemplary embodiment includes the low resistance material 14 in the metal oxide layer 10, and in other words, the thickness of the metal oxide layer 10 is not reduced. For example, the forming voltage can be lowered without increasing the leakage current.

(Low resistance state and high resistance state)
Next, the variable resistance elements 1 a and 1 b after forming the variable resistance element 1 and forming the filament 15 in the metal oxide layer 10 will be described with reference to FIGS. 2 (a) and 2 (b). To do. 2A is a cross-sectional view showing the configuration of the variable resistance element 1a in the low resistance state after forming, and FIG. 2B is a cross section showing the configuration of the variable resistance element 1b in the high resistance state after forming. FIG.

  As shown in FIG. 2A, in the variable resistance element 1a, after the filament 15 is formed in the metal oxide layer 10 by forming, a threshold voltage (hereinafter referred to as a set voltage) for the set operation is set. By applying to the electrodes 11 and 12, the filament 15 connects the low resistance state 14 and the electrode 12, and as a result, the variable resistance element 1a enters the low resistance state. On the other hand, as shown in FIG. 2B, after the filament 15 is formed, the filament 15 is broken by applying a threshold voltage for reset operation (hereinafter referred to as a reset voltage) to the electrodes 11 and 12. The portion 16 breaks, and as a result, the variable resistance element 1b enters a high resistance state.

(Modification of low resistance 14)
In the variable resistance element 1 shown in FIG. 1, the low resistance 14 is in contact with the electrode 11 and is not in contact with the electrode 12, but the structure shown in FIG. 3 may be used. FIG. 3 is a cross-sectional view showing a configuration of the variable resistance element 2, which is a modification of the variable resistance element 1.

  As shown in FIG. 3, the variable resistance element 2 is different from the variable resistance element 1 in that a low resistance that is not in contact with both the electrodes 11 and 12 in the metal oxide layer 10 instead of the low resistance object 14. The thing 24 is provided. As shown in the figure, the low-resistance object 24 is separated from the electrode 11 by a distance d2, and is separated from the electrode 12 by a distance d3.

  When the variable resistance element 2 is formed, the film thickness that determines the forming voltage is the sum of the distance d1 and the distance d2 in the figure, and the forming voltage can be lowered compared to the case where the low resistance object 24 is not provided. it can. Note that the leakage current in the variable resistance element 2 can be suppressed for the same reason as in the case of the variable resistance element 1 in FIG.

  Next, the variable resistance elements 2a and 2b after forming the filament 15 in the metal oxide layer 10 after forming the variable resistance element 2 will be described with reference to FIGS. 4 (a) and 4 (b). explain. 4A is a cross-sectional view showing a configuration of the variable resistance element 2a in the low resistance state after forming, and FIG. 4B is a cross section showing a configuration of the variable resistance element 2b in the high resistance state after forming. FIG.

  As shown in FIG. 4A, in the variable resistance element 2a, a filament 15 is formed in the metal oxide layer 10 from the low resistance material 14 toward both the electrode 11 and the electrode 12 by forming. After the filament 15 is formed, the filament 15 is connected between the electrode 11 and the low resistance state 14 and between the electrode 12 and the low resistance material 14 by applying a set voltage to the electrodes 11 and 12. As a result, the variable resistance element 2a is in a low resistance state. On the other hand, as shown in FIG. 4B, after the filament 15 is formed, the reset voltage is applied to the electrodes 11 and 12, whereby the filament 15 is broken at the filament breakage portion 16. As a result, the variable resistance element 2b is High resistance state. In FIG. 4B, the filament breakage portion 16 is shown in the filament 15 that connects the electrode 12 and the low resistance object 14, but in the filament 15 that connects the electrode 11 and the low resistance object 14. Or may be present in the filaments 15 on both the electrodes 11 and 12 side.

  In the variable resistance elements 1 and 2, in the film thickness direction of the metal oxide layer 10 (the normal direction of the boundary surface between the electrodes 11 and 12 and the metal oxide layer 10), the continuous low resistance region 14 or Although 24 shows the case where there is only one, this is for ease of explanation, and a plurality of 24 may exist. Also in this case, it is clear that there is no change in the effect of locally reducing the thickness of the metal oxide layer 10, that is, the effect of reducing the forming voltage without increasing the leakage current. Furthermore, although the low resistance region 14 is formed so as to be in contact with the electrode 11, it may be formed so as to be in contact with the electrode 12. In addition, the variable resistance element according to the present invention may be configured to include both the low resistance object 14 in contact with the electrode 11 and the low resistance object 14 in contact with the electrode 12, and the variable resistance element is formed. In this case, the filament 15 is formed between the low resistance 14 in contact with the electrode 11 and the low resistance 14 in contact with the electrode 12. Also in this case, the effect of locally reducing the thickness of the metal oxide layer 10, that is, the effect of reducing the forming voltage without increasing the leakage current remains unchanged.

(Manufacturing method of variable resistance element)
Next, a method for manufacturing a variable resistance element before forming according to the present invention will be described with reference to FIGS. 5A to 5E are cross-sectional views showing the configuration of the variable resistance element in each manufacturing process.

  First, as shown in FIG. 5A, a Ti layer 19 and a Pt layer 12 as a lower electrode (corresponding to the electrode 12 in FIG. 1) are formed on an Si substrate 17 with a silicon oxide film 18 by RF magnetron sputtering. Then, the metal oxide layer 10 is deposited in this order to form a laminated structure of Ti / Pt / metal oxide layer. Here, the Ti layer 19 serves as an adhesive for improving the adhesion between the Pt layer 12 as the lower electrode and the substrate 17 with the silicon oxide film 18. The film was formed under the condition that the substrate temperature was room temperature by using Ar 100% gas having an RF output of 200 W and a pressure of 0.5 Pa. Next, the Pt layer 12 is formed by using an Ar 100% gas with an RF output of 100 W and a pressure of 0.3 Pa under the condition that the substrate temperature is room temperature.

The metal oxide layer 10 is deposited by depositing the substrate at room temperature in an Ar atmosphere with an RF output of 200 W and a gas pressure of 0.5 Pa. The composition of the metal oxide layer 10 can be controlled by appropriately adding O ₂ gas.

  The metal oxide layer 10 is composed of an oxide of at least one metal selected from Co, Ni, Ti, V, Cu, W, Nb, and Mn. The film thickness of the metal oxide layer 10 may be set as appropriate so that the leakage current flowing through the metal oxide layer 10 is a predetermined value or less, and may be 50 nm, for example.

  Next, as shown in FIG. 5B, element isolation is performed by photolithography using an i-line reduction projection exposure apparatus and Ar ion milling. Ar ion milling is performed at an applied voltage of 300V. In addition, as photolithography used in the present embodiment, other methods such as electron beam drawing can be used. Next, after Ar ion milling, the remaining photoresist 20 is removed to expose the metal oxide layer 10.

  Next, as shown in FIG. 5C, another photoresist 21 different from the photoresist 20 is applied to the Pt layer 12 and the metal oxide layer 10. Further, a metal layer as the upper electrode 11 and a Pt layer 22 as a capping layer are sequentially deposited from above in the drawing by RF magnetron sputtering. Thereby, as shown in the figure, a portion where the upper electrode 11 and the Pt layer 22 are laminated on the metal oxide layer 10 and a portion where the upper electrode 11 and the Pt layer 22 are laminated on the photoresist 21. And can be divided into In addition, for the film formation of the metal layer as the upper electrode 11, a deposition process was performed using an RF magnetron sputtering method in an Ar atmosphere at a substrate temperature of room temperature. The thickness of the metal layer as the upper electrode 11 is, for example, 50 nm. Further, the film formation of the Pt layer 22 as the capping layer for preventing oxidation is performed by the same method as the film formation of the Pt layer of the lower electrode 12.

  Next, as shown in FIG. 5D, the photoresist 21 is removed together with the upper electrode 11 and the Pt layer 22 deposited on the photoresist 21 to expose the Pt layer as the lower electrode 12.

  Next, heat treatment is used to form the low resistance material 14 shown in FIG. Specifically, the low resistance material 14 can be formed in the metal oxide layer 10 by diffusing elements constituting the upper electrode 11 into the metal oxide layer 10 by heat treatment. Note that the diffused element itself constituting the upper electrode 11 may form the low resistance substance 14, or the diffused element and the element constituting the metal oxide layer 10 are reacted to form the low resistance substance 14. You may let them. For example, the diffused element can take oxygen from the metal oxide constituting the metal oxide layer 10 and reduce it to form the low resistance material 14.

  The metal oxide layer 10 is more preferably polycrystalline. If it is polycrystalline, it becomes easy to form the low resistance region 14 locally by utilizing grain boundary diffusion. In the case of polycrystal, the low resistance region 14 can also be formed by precipitating a metal at the grain boundary of the metal oxide constituting the metal oxide layer 10 by heat treatment. Note that the cross-sectional shape of the variable resistance element shown in FIG. 5D is for the convenience of manufacturing the variable resistance element and the simplicity of the experiment, and the cross-sectional shape shown in FIG. It is not limited. In addition to the above, the film forming method used in the variable resistance element manufacturing method according to the present invention includes well-known methods such as laser ablation, chemical vapor deposition (CVD), and metal (surface) oxidation. Available.

(Comparison with reference example)
The variable resistance element manufactured by the method described with reference to FIGS. 5A to 5E, in other words, heat-treated and the low-resistance element 14 is formed in the metal oxide layer 10, and heat-treatment are performed. FIG. 6 shows a comparison result of the current-voltage characteristics at the time of forming in the variable resistance element in which the low resistance material 14 is not formed in the metal oxide layer 10. Note that the heat treatment performed for manufacturing the variable resistance element is performed at a temperature of 300 ° C. for 10 minutes under a reduced pressure of Ar atmosphere of 0.5 Pa.

  FIG. 6 is a graph showing current-voltage characteristics during forming of a variable resistance element with heat treatment and a variable resistance element without heat treatment. In the graph shown in FIG. 6, the horizontal axis represents the potential difference applied between the two electrodes of the variable resistance element, and the vertical axis represents the current value flowing through the variable resistance element.

  As shown in FIG. 6, in the variable resistance element not subjected to heat treatment, the forming voltage necessary for forming is about 10V. On the other hand, in the variable resistance element subjected to the heat treatment, the forming voltage is about 3.5 V, and it can be seen that the forming voltage can be lowered by about 1/3 as compared with the variable resistance element not subjected to the heat treatment. In addition, the current flowing through the variable resistance element that has undergone heat treatment after forming does not increase significantly compared to the current that flows through the variable resistance element that has not undergone heat treatment after forming. It can be seen that the forming voltage can be lowered while suppressing the leakage current. In measuring the current-voltage characteristics shown in FIG. 6, at the time of forming, a current limiting resistor of 100 kΩ is inserted in series in the variable resistance element. This is to prevent the variable resistance element from being destroyed due to a large current flowing during forming.

  Next, FIG. 7 shows current-voltage characteristics in the variable resistance element during forming and when a set voltage and a reset voltage having different polarities are applied to the variable resistance element after forming. FIG. 7 shows a case where a positive forming voltage is applied to the heat-treated variable resistance element to bring it to a low resistance state, a negative reset voltage is applied to the variable resistance element, and then a positive set voltage is applied. Is a graph showing current-voltage characteristics in the variable resistance element when a negative reset voltage is applied to the variable resistance element again. In the graph shown in FIG. 7, the horizontal axis represents the potential difference applied between two electrodes of the variable resistance element, and the vertical axis represents the current value flowing through the variable resistance element.

  Here, after the forming, in the variable resistance element that has been subjected to heat treatment, the set operation and the reset operation are repeatedly performed alternately, and the variable at the time of applying the read voltage (0.2 V) immediately after each set operation and each reset operation. A change in the value of the current flowing through the resistance element will be described with reference to FIG. FIG. 8 shows a change in the value of the current flowing through the variable resistance element when the read voltage is applied immediately after the set operation and immediately after the reset operation by performing a set operation and a reset operation with a positive set voltage and a negative reset voltage. It is a graph to show. In the switching cycle on the horizontal axis in FIG. 8, the odd-numbered cycle indicates the time immediately after the forming or setting operation, and the even-numbered cycle indicates the time immediately after the reset operation.

  As shown in FIG. 8, when the current value flowing through the variable resistance element when the read voltage is applied immediately after the reset operation is compared with the current value flowing through the variable resistance element when the read voltage is applied immediately after the set operation, the resistance change The ratio is two digits or more, and it can be seen that there is no problem that the resistance change ratio is lowered in the variable resistance element subjected to the heat treatment.

  Next, FIG. 9 shows current-voltage characteristics of the variable resistance element when the forming voltage, the set voltage, and the reset voltage are all voltages having the same polarity (positive voltage). FIG. 9 shows the current-voltage characteristics of the variable resistance element when each operation is performed in the order of forming, reset operation, set operation, reset operation, set operation, and reset operation on the heat-treated variable resistance element. It is a graph which shows. In the graph shown in FIG. 9, the horizontal axis represents the potential difference applied between two electrodes of the variable resistance element, and the vertical axis represents the current value flowing through the variable resistance element.

  Here, after the forming, in the variable resistance element that has been subjected to heat treatment, the set operation and the reset operation are repeatedly performed alternately, and the variable at the time of applying the read voltage (0.2 V) immediately after each set operation and each reset operation. A change in the value of the current flowing through the resistance element will be described with reference to FIG. FIG. 10 is a graph showing changes in the value of the current flowing through the variable resistance element when the read voltage is applied immediately after the set operation and immediately after the reset operation when the set operation and the reset operation are performed with a positive set voltage and a reset voltage. It is. In the switching cycle on the horizontal axis in FIG. 10, the odd-numbered cycle indicates the time immediately after the forming or setting operation, and the even-numbered cycle indicates the time immediately after the reset operation.

  As shown in FIG. 10, when the current value flowing through the variable resistance element when the read voltage is applied immediately after the reset operation is compared with the current value flowing through the variable resistance element when the read voltage is applied immediately after the set operation, the resistance change The ratio is two digits or more, and it can be seen that there is no problem that the resistance change ratio is lowered in the variable resistance element subjected to the heat treatment.

  In measuring the current-voltage characteristics shown in FIG. 7 and FIG. 9, and in measuring the current when the read voltage is applied in the reset operation and the set operation of FIG. 8 and FIG. The measurement is performed by inserting a 100 kΩ current limiting resistor in series with the variable resistance element. This is to prevent the variable resistance element from being destroyed due to a large current flowing during forming.

  Next, a TEM image obtained by photographing a cross section of a variable resistance element not subjected to heat treatment (corresponding to a variable resistance element according to the prior art) and a heat treated variable resistance element with a transmission electron microscope (TEM). Is shown in FIGS. 11 (a) and 11 (b). FIG. 11A is a drawing showing a TEM image of a variable low resistance element not subjected to heat treatment, and FIG. 11B is a drawing showing a TEM image of the variable resistance element subjected to heat treatment.

  The TEM images shown in FIGS. 11A and 11B are obtained by photographing the interface between the metal oxide layer 10 made of nickel oxide and the electrode 11 made of Al (aluminum) with a thickness of 20 nm. . Further, the variable resistance elements of the TEM images in FIGS. 6A and 6B have substantially the same structure as the variable resistance element showing the current-voltage characteristics at the time of forming shown in FIG.

  As shown in FIGS. 11A and 11B, the nickel oxide constituting the metal oxide layer 10 has a columnar crystal structure, and Al in the electric field 11 is likely to cause grain boundary diffusion. Yes. From this, Al in the electrode 11 diffuses into the metal oxide layer 10, and the diffused Al itself, or the nickel that has been diffused and reduced by taking oxygen from the nickel oxide, is the grain boundary of the nickel oxide. It is thought that a low resistance material is generated in the vicinity.

  Next, the element distribution of the variable resistance element not subjected to heat treatment and the element distribution (EELS intensity distribution) of the variable resistance element subjected to heat treatment were measured using electron energy loss spectroscopy (EELS), and the measurement result Is shown in FIGS. 12 (a) and 12 (b). FIG. 12A is a graph showing the element distribution of the variable resistance element not subjected to heat treatment, and FIG. 12B is a graph showing the element distribution of the variable resistance element subjected to heat treatment. In addition, the variable resistance element which is a measurement object of the graph shown to the same figure (a) and (b) is Pt layer which is the lower electrode 12, the nickel oxide layer which is the metal oxide layer 10, and Al which is the upper electrode 11. The layers are formed in the order of the Pt layer, which is the capping layer 22, and have substantially the same structure as the variable resistance element showing the current-voltage characteristics at the time of forming shown in FIG.

  First, in the graph shown in FIG. 12A, two layers of a layer made of nickel, aluminum, and oxygen and an aluminum oxide layer are formed at a portion where nickel oxide and Al are in contact with each other. The nickel oxide layer which is the metal oxide layer 10 has a substantially uniform composition distribution. In FIG. 9A, the layer existing as metal Al cannot be confirmed, but in the sample used for the analysis, the deposited Al was thin and thus all oxidized. In the variable resistance element shown in FIG. 6, a metal Al layer exists.

  On the other hand, FIG. 12B shows the element distribution of the variable resistance element subjected to the heat treatment. Compared with the element distribution of the variable resistance element not subjected to the heat treatment in FIG. Has changed. The distribution of oxygen is uniform, and the EELS signal intensity corresponding to nickel is small near the electrode interface. As a result, an oxygen-excess nickel oxide layer and a layer made of nickel, aluminum, and oxygen are formed in the vicinity of the nickel oxide and electrode interface, in other words, between the metal oxide layer 10 and the electrode 11. Yes. That is, as a result of heat-treating the variable resistance element, the variable resistance element has an oxygen / metal element ratio (nickel of nickel) in the vicinity of the interface between nickel oxide constituting the metal oxide layer 10 and Al constituting the electrode 11. A transition layer composed of a transition region composed of a transition layer having a high transition ratio (the ratio of the number of oxygen atoms to the number of atoms), a metal (Al) that constitutes the electrode 11, a metal (nickel) that constitutes a metal oxide, and oxygen It can be confirmed that the structure has a second region. Therefore, it is considered that the forming voltage can be lowered by performing a treatment that results in such an element distribution.

[Second Embodiment]
Next, a nonvolatile semiconductor memory device 4 (hereinafter referred to as a memory device) according to a second embodiment of the present invention will be described with reference to FIGS.

  First, the configuration of the storage device 4 will be described with reference to FIG. FIG. 13 is a block diagram showing the configuration of the storage device 4.

  As shown in FIG. 13, the storage device 4 includes a memory cell array 40, a bit line decoder 41, a word line decoder 42, a voltage switch circuit 44, a read circuit 45, a voltage generation circuit 46, and a control circuit 43. .

  Here, the internal configuration of the memory cell array 40 will be described below with reference to FIG. FIG. 14 is a schematic diagram showing the configuration of the memory cell array 40.

  As shown in FIG. 14, the memory cell array 40 includes a plurality of variable resistance elements 1 or 2 described in the first embodiment as memory cells 50, and the plurality of memory cells 50 are arranged in a matrix in the row direction and the column direction. It is arranged in a shape. More specifically, the memory cell array 40 includes m bit lines (column selection lines) BL1 to BLm (hereinafter collectively referred to as bit lines BL) extending in the column direction and n extending in the row direction. A cross-point array configuration in which m × n memory cells 50 are arranged at each intersection with one word line (row selection line) WL1 to WLn (hereinafter collectively referred to as word line WL). ing. For example, the electrodes 12 (see FIG. 1) of the memory cells 50 in the same column are connected to each other, the wiring extending in the column direction is used as the bit line BL, and the electrodes 11 (see FIG. 1) of the memory cells 50 in the same row are connected to each other. And the wiring extended in the row direction is defined as a word line WL.

  The bit line decoder 41 and the word line decoder 42 have a function as a memory cell selection circuit that selects the memory cells 50 in units of rows, columns, or memory cells via the bit lines BL and the word lines WL.

  Referring to FIG. 13, the bit line decoder 41 and the word line decoder 42 are memory cells 50 corresponding to an address signal indicating a read target or a rewrite target input to the control circuit 43 via the address line 47. Are selected from the memory cell array 40. More specifically, the word line decoder 42 selects the word line WL of the memory cell array 40 corresponding to the address signal input via the address line 47, and the bit line decoder 41 inputs via the address line 47. The bit line BL of the memory cell array 40 corresponding to the address signal thus selected is selected.

  The control circuit 43 controls each of a rewrite operation (corresponding to a set operation and a reset operation in the first embodiment) of information stored in the memory cell array 40 (hereinafter referred to as storage information) and a read operation of stored information. I do.

  At the time of rewrite operation or read operation of stored information, the control circuit 43 controls the address signal input through the address line 47, the data signal input through the data line 48 (only during the rewrite operation), and control. Based on the control input signal input via the signal line 19, the word line decoder 42, the bit line decoder 41, and the voltage switch circuit 44 are controlled to read or rewrite the stored information stored in the memory cell array 40. . In the storage device 4 shown in FIG. 13, the control circuit 43 has functions as a general address buffer circuit, data input / output buffer circuit, and control input buffer circuit (not shown).

  The voltage switch circuit 44 supplies each voltage of a signal input to the memorial array 40 via the word line WL and the bit line BL, which is required at the time of rewriting operation and reading operation of the storage information stored in the memory cell array 40. It switches according to the operation and functions as a voltage supply circuit that supplies the bit line decoder 41 and the word line decoder 42. In FIG. 13, Vcc is a power supply voltage of the device of the present invention, Vss is a ground voltage, Vpp is a set voltage, Vee is a reset voltage, and Vrd is a read voltage. The power supply voltage Vcc and the ground voltage Vss to the voltage switch circuit 44 are supplied from the outside of the storage device 4. In addition, each voltage of a signal input to the memory cell array 40 in the set operation, the reset operation, and the read operation is generated by the voltage generation circuit 46 from the power supply voltage Vcc or another power supply voltage.

  The read circuit 45 converts the read current flowing through the selected bit line BL selected by the bit line decoder 41 out of the read current flowing through the bit line BL connected to the selected memory cell 50 indicated by the address signal. Further, the voltage-converted signal is determined in the memory information state of the memory cell 50 to be read connected to the selected bit line BL in the selected memory cells in one row, and the result is transferred to the control circuit 43 for control. The circuit 43 outputs the signal transferred from the reading circuit 45 to the data line 48.

  Next, an example of voltage application to the memory cell array 40 during the rewrite operation will be described. In the present embodiment, the variable resistance element 1 or 2 (see FIG. 1 or 3) used in the memory cell 50 has switching characteristics as shown in FIGS. Therefore, when a voltage pulse having a positive set voltage is applied to the electrode 11 with the electrode 12 as a reference, the electric resistance of the variable resistance element is switched from the high resistance state to the low resistance state. On the contrary, when a voltage pulse of a negative reset voltage is applied to the electrode 11 with the electrode 12 as a reference, the electric resistance of the variable resistance element is switched from the low resistance state to the high resistance state. In the following description, it is assumed that the switching operation does not occur when the applied voltage pulse has a voltage amplitude that is half of the set voltage and the reset voltage.

  Here, at the time of the set operation, the bit line decoder 41 and the word line decoder 42 select that the ground voltage Vss (0 V) is connected to the selected memory cell 50 to the selected bit line BL connected to the selected memory cell 50 to be rewritten. A set voltage Vpp is applied to each word line WL. Thus, the set operation is performed by applying the set voltage Vpp to the electrode 11 (selected word line WL side) with the electrode 12 (selected bit line BL side) of the selected memory cell 50 as a reference. At this time, the bit line decoder 41 and the word line decoder 42 are half the set voltage Vpp (Vpp / 2) with respect to the unselected bit line BL and the unselected word line WL that are not connected to the selected memory cell 50. ) Is applied. Thus, no voltage is applied to both ends of the first unselected memory cell 50 connected to the unselected bit line BL and the unselected word line WL, respectively, and the first bit line is connected to the selected bit line BL and the unselected word line WL. On both ends of the second non-selected memory cell 50 and on both ends of the third non-selected memory cell 50 respectively connected to the non-selected bit line BL and the selected word line WL, A positive voltage (Vpp / 2) that is half the set voltage is applied, and as a result, no set operation occurs in any unselected memory cell 50.

  During the reset operation, the bit line decoder 41 and the word line decoder 42 apply the reset voltage Vee to the selected word line WL connected to the selected memory cell 50 and the selected bit line BL connected to the selected memory cell 50 to be rewritten. The ground voltage Vss is applied. Thereby, with the electrode 12 (selected bit line BL side) of the selected memory cell 50 as a reference, the negative reset voltage (−Vee) is applied to the electrode 11 (selected word line WL side), and the reset operation is executed. The At this time, the bit line decoder 41 and the word line decoder 42 are half the reset voltage Vee (Vee / 2) with respect to the unselected bit line BL and the unselected word line WL that are not connected to the selected memory cell 50. ) Is applied. Thus, no voltage is applied to both ends of the first unselected memory cell 50 connected to the unselected bit line BL and the unselected word line WL, respectively, and the first bit line is connected to the selected bit line BL and the unselected word line WL. On both ends of the second non-selected memory cell 50 and on both ends of the third non-selected memory cell 50 respectively connected to the non-selected bit line BL and the selected word line WL, As a result, a negative voltage (−Vee / 2) that is half of the reset voltage is applied, and as a result, no reset operation occurs in any unselected memory cell 50.

  Next, an example of voltage application to the memory cell array 40 during the read operation will be described. During the read operation, the bit line decoder 41 and the word line decoder 42 are connected to the selected bit line BL connected to the selected memory cell 50 to be read, the read voltage Vrd is grounded to the selected word line WL connected to the selected memory cell 50. A voltage Vss (0 V) is applied. As a result, the read voltage (Vrd) is applied to the electrode 12 (selected bit line BL side) with the electrode 11 (selected word line WL side) of the selected memory cell 50 as a reference. At this time, a read current corresponding to the resistance state flows through the selected memory cell 50 from the selected bit line BL to the selected word line WL. A read operation is performed when the read circuit 45 detects this read current via the bit line decoder 41.

  In the second embodiment, the word line is connected to the electrode 11 and the bit line is connected to the electrode 12, but conversely, the bit line is connected to the electrode 11 and the word line is connected to the electrode 12. Good. In the read operation, the read circuit 45 is connected to the bit line decoder 41, but the read circuit 45 may be connected to the word line decoder 42.

  Further, in the second embodiment, the 1R type memory cell using only the variable resistance element described in the first embodiment is assumed as the configuration of the memory cell 50. However, the present invention is not limited to this. 1T / 1R type memory cell configuration in which a variable resistance element and a rectifying element such as a diode are connected in series, or a 1T / 1R configured by a series circuit of a variable resistance element and a selection transistor (such as a MOSFET or a bipolar transistor). The memory cell array may be configured with a type of memory cell configuration.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  In addition, you may comprise the variable resistance element of this invention, its manufacturing method, and the non-volatile memory device provided with this variable resistance element as a memory | storage layer as follows.

(First configuration)
A metal oxide layer is provided between the first electrode and the second electrode, and the electrical resistance between the first and second electrodes is reversible in response to an electrical stress applied between the first and second electrodes. The variable resistance element is a variable resistance element, characterized in that a low resistance region having a resistivity partially lower than that of the surrounding is provided in the metal oxide layer.

(Second configuration)
The variable according to the first configuration, wherein the low-resistance region is composed of at least one element constituting at least one specific electrode of the first electrode and the second electrode. Resistance element.

(Third configuration)
The variable resistance element according to the first configuration, wherein the low resistance region is composed of at least one element constituting the metal oxide layer.

(Fourth configuration)
The variable resistance element according to the second configuration or the third configuration, wherein the low resistance region exists in the vicinity of a grain boundary of the metal oxide layer.

(Fifth configuration)
A metal oxide layer is provided between the first electrode and the second electrode, and the electrical resistance between the first and second electrodes is reversible in response to an electrical stress applied between the first and second electrodes. The variable resistance element is a method for manufacturing a variable resistance element, wherein the low resistance region is formed in the metal oxide layer by a diffusion step of diffusing elements constituting the specific electrode. Device manufacturing method.

(Sixth configuration)
6. The method of manufacturing a variable resistance element according to claim 5, wherein the diffusion step is performed by heat treatment.

(Seventh configuration)
The memory cell having the variable resistance element according to any one of the first configuration to the fourth configuration, and electric power is applied to both ends of the variable resistance element to change the electrical resistance, thereby Information rewriting means for performing writing and erasing, information reading means for applying a read voltage to both ends of the variable resistance element, detecting an electrical resistance state from the amount of current flowing through the variable resistance element, and reading stored information; A non-volatile semiconductor memory device comprising:

  The present invention provides a variable resistance element capable of reducing a forming voltage required for forming while suppressing leakage current, a method for manufacturing the same, and a nonvolatile memory device including the variable resistance element as a memory cell. In particular, it can be used in a portable or portable memory.

DESCRIPTION OF SYMBOLS 1 Variable resistance element 1a Variable resistance element 1b Variable resistance element 2 Variable resistance element 2a Variable resistance element 2b Variable resistance element 11 Electrode (1st electrode)
12 electrodes (second electrode)
14 Low Resistance 24 Low Resistance 4 Nonvolatile Semiconductor Memory Device 40 Memory Cell 41 Bit Line Decoder (Data Writing Unit, Data Reading Unit)
42 Word line decoder (data writing means, data reading means)
45 Reading circuit (data reading means)

Claims (5)

A first electrode and a second electrode; and a metal oxide sandwiched between the first electrode and the second electrode, the first electrode depending on a voltage applied between the first electrode and the second electrode. A variable resistance element in which the electrical resistance between the electrode and the second electrode reversibly changes,
Between at least one of the first electrode and the second electrode and the metal oxide, in order from the metal oxide side,
A first region composed of a first metal element constituting the metal oxide and oxygen and having a high ratio of the number of oxygen atoms to the number of atoms of the first metal element;
A second region that is adjacent to the first region and that includes at least one of the first electrode and the second electrode, the second metal element, the first metal element, and oxygen. When,
A variable resistance element comprising:   The variable resistance element according to claim 1, wherein the second metal element is aluminum.   The variable resistance element according to claim 1, wherein the metal oxide is nickel oxide. A first electrode and a second electrode; and a metal oxide layer made of a metal oxide sandwiched between the first electrode and the second electrode, and applied between the first electrode and the second electrode. A variable resistance element in which an electrical resistance between the first electrode and the second electrode reversibly changes according to a voltage;
In the metal oxide layer, a low-resistance material having a lower electrical resistance than the metal oxide and separated from at least one of the first electrode and the second electrode, and at least one constituting the metal oxide It further comprises a low resistance material composed of various metal elements ,
The metal oxide is polycrystalline,
The variable resistance element , wherein the low-resistance material is composed of the metal element deposited at a grain boundary of the metal oxide . After forming by applying a voltage between the first electrode and the second electrode, the electrical resistance reversibly changes according to the voltage applied between the first electrode and the second electrode. The variable resistance element according to claim 4 .