# Patent

## Title
Hetero-switching layer in a RRAM device and method

## Abstract

A non-volatile memory device structure includes first electrodes comprising conductive silicon-containing material, a plurality of resistive switching material stacks comprising first resistive switching material and second resistive switching material overlying the first electrode, wherein the first resistive switching material comprises a first resistance switching voltage and the second resistive switching material comprises a second resistance switching voltage less than the first amplitude, second electrodes comprising metal material overlying and electrically coupled to the plurality of resistive switching material stacks, wherein a plurality of memory elements are formed from the first plurality of electrodes, the plurality of resistive switching material stacks, and the second plurality of electrodes.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. application Ser. No. 13/290,024, filed Nov. 4, 2011, now U.S. Pat. No. 8,467,227 issued Jun. 18, 2013, which is a non-provisional of U.S. Application No. 61/410,035, filed Nov. 4, 2010, and claims priority thereto. This application also claims priority to U.S. application Ser. No. 13/585,759, filed Aug. 14, 2012, now U.S. Pat. No. 8,569,172 issued Oct. 29, 2013; U.S. Application No. 61/712,171, filed Oct. 10, 2012, and U.S. Application No. 61/786,100, filed Mar. 15, 2013. These cited documents are incorporated by reference herein, for all purposes.


STATEMENTS RELATED TO FEDERAL OR GOVERNMENT SPONSORED RESEARCH
Not Applicable
BACKGROUND
The present invention is related to switching devices. More particularly, the present invention provides a resistive switching device characterized by a controllable programming current with faster operation speed. Embodiments of the present invention have been applied to fabrication and operation of a resistive random access memory device. But it should be recognized that the present invention can have a much broader range of applicability.
The success of semiconductor devices has been mainly driven by an intensive transistor down-scaling process. However, as field effect transistors (FET) approach sizes less than 100 nm, problems such as short channel effect can degrade device performance. Moreover, such sub 100 nm device size can lead to sub-threshold slope non-scaling and also increases power dissipation. It is generally believed that transistor-based memories such as those commonly known as Flash may approach an end to scaling within a decade.
Other non-volatile random access memory devices such as ferroelectric RAM (Fe RAM), magneto-resistive RAM (MRAM), organic RAM (ORAM), and phase change RAM (PCRAM), among others, have been explored as next generation memory devices. These devices often require new materials and device structures to couple with silicon-based devices to form a memory cell, which lack one or more key attributes. For example, FeRAM and MRAM devices have fast switching characteristics and good programming endurance, but their fabrication is not CMOS compatible and size is usually large. Switching for a PCRAM device requires a high power. Organic RAM is incompatible with large volume silicon-based fabrication and device reliability is usually poor. Desirable attributes of a high density device should include high switching speed, reliable switching, and high endurance, among others.
From the above, a new semiconductor device structure and integration is desirable.
BRIEF SUMMARY OF THE PRESENT INVENTION
The present invention is directed to switching device. More particularly, the present invention is directed to a resistive switching device having more than one switching material to enhance performance of the resistive switching device. For example, the resistive switching device can include a first switching material for switching and a second material for suppressing leakage current when an operating voltage is applied. Embodiments according to the present invention can be particularly useful for a non-volatile memory device in an interconnected device array. It should be recognized, however, that embodiments according to the present invention can have a much broader range of applicability.
In a specific embodiment, a non-volatile memory device structure is provided. The non-volatile memory device includes a first electrode, a second electrode, and a resistive switching material stack sandwiched between the first electrode and the second electrode. In a specific embodiment, the resistive switching material stack overlies the first electrode. The resistive switching material stack includes a first resistive switching material and a second resistive switching material. In a specific embodiment, the second switching material overlying the first electrode and the first switching material overlying the second switching material. In a specific embodiment, the first switching material is characterized by a first switching voltage having a first amplitude. The second resistive switching material is characterized by a second switching voltage having a second amplitude no greater than the first switching voltage. In a specific embodiment, the second electrode includes at least a metal material overlying the first switching material, and physically and electrically in contact with the first resistive switching material.
In a specific embodiment, a method for writing to a resistive switching device is provided. The method includes providing a resistive switching device. The resistive switching device includes a first electrode, a switching material stack comprising a first switching material and a second switching material, and a second electrode. In a specific embodiment, the second switching material overlies the first electrode, the first switching material overlies the second switching material, and the second electrode comprising at least a metal material overlies the first switching material. The first switching material is characterized by a first switching voltage having a first amplitude. The second switching material is characterized by a second switching voltage. In a specific embodiment, the first amplitude is greater than the second amplitude. In a specific embodiment, the method includes applying a first voltage to the second electrode to cause the first switching material to change from a first high resistance state to a first low resistant state.
In a specific embodiment, a method for erasing of a resistive switching device after write is provided. The method includes providing a resistive switching device in a write state. The resistive switching device includes a first electrode, a switching material stack comprising a first switching material and a second switching material, and a second electrode. In a specific embodiment, the second switching material overlies the first electrode, the first switching material overlies the second switching material, and the second electrode comprising at least a metal material overlies the first switching material. The first switching material is characterized by a first switching voltage having a first amplitude. The second switching material is characterized by a second switching voltage. In a specific embodiment, the first amplitude is greater than the second amplitude. In a specific embodiment, the write state is caused at least by a low resistance state of the first switching material. The method includes applying a first voltage more negative than an erase voltage of the first resistive switching material to cause at least the first switching material to be in a first high resistance state and to cause the resistive switching device to change from the write state to an erased state.
In a specific embodiment, a method to read a state of a resistive switching device is provided. The method includes providing a resistive switching device. The resistive switching device includes a first electrode, a switching material stack comprising a first switching material and a second switching material, and a second electrode. In a specific embodiment, the second switching material overlies the first electrode, the first switching material overlies the second switching material, and the second electrode comprising at least a metal material overlies the first switching material. The first switching material is characterized by a first switching voltage having a first amplitude. The second switching material is characterized by a second switching voltage. In a specific embodiment, the first amplitude is greater than the second amplitude. The method includes applying a read voltage to the second electrode, the read voltage is configured to cause the second switching material to change from a first high resistance state to a first low resistance state while maintaining a resistance state of the first switching material. The method includes determining a read current flowing in the resistive switching device to determine the state of the resistive switching device in a specific embodiment.
In a specific embodiment, a method for suppressing a leak current in a resistive switching device is provided. The method includes providing a resistive switching device. The resistive switching device includes a first electrode, a switching material stack comprising a first switching material and a second switching material, and a second electrode. In a specific embodiment, the second switching material overlies the first electrode, the first switching material overlies the second switching material, and the second electrode comprising at least a metal material overlies the first switching material. The first switching material is characterized by a first switching voltage having a first amplitude. The second switching material is characterized by a second switching voltage. In a specific embodiment, the first amplitude is greater than the second amplitude. The method includes applying a first voltage to the second electrode, the first voltage being configured to cause the second switching material to be at a high resistance state and maintaining the first switching material to be at a low resistance state, the high resistance state suppressing a leak current from applying the first voltage.
In a specific embodiment, a non-volatile memory device structure is provided. The non-volatile memory device structure includes a first electrode configured to extend in a first direction. The non-volatile memory device structure includes a first structure configured to extend in a first direction. In a specific embodiment, the first structure includes a stack of switching material spatially configured to extend in a second direction at an angle to the first direction. In a specific embodiment, the stack of switching material includes a first switching material overlying the first electrode. The first switching material includes a solid electrolyte material in a specific embodiment. The stack of switching material includes a second switching material overlying the first switching material. In a specific embodiment, the second switching material includes an amorphous silicon material in a specific embodiment. The non-volatile memory device structure further includes a second electrode comprising at least a portion comprising a metal material in contact with the amorphous silicon material in a specific embodiment.
In a specific embodiment, a non-volatile memory device structure is provided. The non-volatile memory device structure includes a first structure spatially configured to extend in a first direction. In a specific embodiment, the first structure includes a first electrode, a solid electrolyte material overlying the first electrode and an amorphous silicon material overlying the solid electrolyte material. The non-volatile memory device structure includes a second electrode spatially configured to extend in a second direction at an angle to the first direction. In a specific embodiment, the second electrode includes at least a first portion directly in contact with the amorphous silicon material and a second portion for an interconnect structure.
In a specific embodiment, a non-volatile memory device structure is provided. The non-volatile memory device structure includes a first electrode spatially configured to extend in a first direction, a second electrode spatially configured to extend in a second direction perpendicular to the first direction, and a first structure disposed in an intersection region formed between the first electrode and the second electrode. In a specific embodiment, the first structure includes a solid electrolyte material overlying the first electrode and an amorphous silicon material overlying the solid electrolyte material. In a specific embodiment, the second electrode includes at least a metal material in direct contact with the amorphous silicon material.
Additional aspects include a method of reading a resistive switching device in a crossbar array, comprising: providing a first switching device, a second switching device, a third switching device, and a fourth switching device, the first switching device being in a first resistance state, each of the first switching device, the second switching device, the third switching device, and the fourth switching device comprising at least a first switching material and a second switching material, the first switching material being characterized by a first on voltage and a first off voltage and the second switching material being characterized by a second on voltage and a second off voltage, the first on voltage being greater than the second on voltage, the first off voltage being greater than the second off voltage; applying a read voltage to the first switching device, the read voltage being configured to maintain the second switching material of at least one of the second switching device, the third device and the fourth device to be at a high resistance state, the high resistance state suppressing a leakage current from at least one of the second switching device, the third device and the fourth device to flow in the first switching device; and measuring a read current in the first switching device caused by the read voltage to determine the first resistance of the first switching device.
Additional aspects include the method of above wherein the first on voltage causes the first switching material to change from a first high resistance state to a first low resistance state and the first off voltage causes the first switching material to change from the first low resistance state to a first high resistance state.
Additional aspects include the method of above wherein the second on voltage causes the second switching material to change from a second high resistance state to a second low resistance state and the second off voltage causes the second switching material to change from the second low resistance state to a second high resistance state.
Additional aspects include the method of above wherein the read voltage is configured to be greater than the second on voltage and no greater than three times the second first on voltage to maintain the second switching material of at least one of the second switching device, the third device and the fourth device to be at the high resistance state.
Additional aspects include a non-volatile memory device structure comprising: a first electrode configured to extend in a first direction; and a first structure comprising a stack of material spatially configured to extend in a second direction at an angle to the first direction, the stack of material comprising: a solid electrolyte material overlying the first electrode; an amorphous silicon material overlying the solid electrolyte material; and a second electrode comprising at least a portion comprising a metal material in contact with the amorphous silicon material.
Additional aspects include a non-volatile memory device structure comprising: a first structure spatially configured to extend in a first direction, the first structure comprising: a first electrode; a solid electrolyte material overlying the first electrode; an amorphous silicon material overlying the solid electrolyte material; and a second electrode spatially configured to extend in a second direction at an angle to the first direction, the second electrode comprising at least a first portion directly in contact with the amorphous silicon material and a second portion for an interconnect structure.
Additional aspects include a non-volatile memory device structure comprising: a first electrode spatially configured to extend in a first direction; a second electrode spatially configured to extend in a second direction, the second direction being perpendicular to the first direction; and a first structure disposed in an intersection region formed between the first electrode and the second electrode, the first structure comprising: a solid electrolyte material overlying the first electrode; an amorphous silicon material overlying the solid electrolyte material.
Additional aspects include a method for suppressing a leak current in a resistive switching device, comprising: providing a resistive switching device, the resistive switching device comprising a first electrode, a switching material stack comprising a first switching material and a second switching material, the second switching material overlying the first electrode, the first switching material overlying the second switching material, and a second electrode comprising at least a metal material overlying the first switching material, the first switching material being characterized by a first switching voltage, the second switching material being characterized by a second switching voltage, the first switching voltage being characterized by a first amplitude and the second switching device being characterized by a second amplitude, the first amplitude being greater than the second amplitude; and applying a first voltage to the second electrode, the first voltage being configured to cause the second switching material to be at a high resistance state and maintaining the first switching material to be at a low resistance state, the high resistance state suppressing a leak current from applying the first voltage.
Additional aspects includes a method according to the above wherein the first voltage is no greater than an on voltage for the first switching material and less negative than an off voltage for the second switching material.
Many benefits can be achieved by ways of the present invention. Embodiments according to the present invention provide a device structure to form a non-volatile memory device that has leakage current suppressed or eliminated, which is essential for a crossbar array of memory cells. The device structure further provides desirable characteristics for write, read, and erase and allowing fabrication of a memory device having a high on state current and desirable data retention characteristic. Additionally, the present device uses materials and techniques that are compatible with current CMOS processing. Depending on the embodiment, one or more of these benefits may be achieved. One skilled in the art would recognize other variations, modifications, and alternatives.



SUMMARY OF THE DRAWINGS
FIG. 1 is a simplified diagram illustrating a device structure for a resistive switching device according to an embodiment of the present invention.
FIG. 2 is a simplified diagram illustrating mechanism of switching for a first switching device.
FIG. 2A is a simplified current versus voltage characteristic of the first switching device.
FIG. 3 is a simplified diagram illustrating mechanism of switching for a second switching device.
FIG. 3A is a simplified current versus voltage characteristic of the second switching device.
FIGS. 4, 4A, 5, 5A, 6, 6A, 7, 7A, 8, 8A are simplified diagrams illustrating mechanism of switching for a switching device according to embodiments of the present invention.
FIG. 9 is a simplified diagram illustrating voltage pulse for turning on the switching device according to an embodiment of the present invention.
FIGS. 10 illustrates short voltage pulse for read of the switching device and corresponding voltage versus current characteristic according to an embodiment of the present invention.
FIG. 11 is a simplified voltage versus current plot illustrating leakage current suppression in the switching device according to an embodiment of the present invention.
FIG. 12 is a simplified diagram illustrating a crossbar array of switching devices according to an embodiment of the present invention.
FIG. 13-15 are simplified diagrams illustrating various device structures for fabricating a switching device for implementing in a crossbar array according to embodiments of the present invention.



DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention is directed to switching device. More particularly, the present invention is directed to a resistive switching device having more than one switching material to enhance performance of the resistive switching device. For example, the resistive switching device can include a first switching material for switching and a second material for suppressing leakage current when an operating voltage is applied. Embodiments according to the present invention can be particularly useful for a non-volatile memory device in an interconnected device array. It should be recognized that embodiments according to the present invention can have a much broader range of applicability.
High density and low cost storage devices are in ever increasing demand due to the growth in consumer devices common in the market place. Current non-volatile memory devices including Flash are probably at an end to further scaling due to fundamental limitations in the devices. It is predicted that current charge storage in a floating gate or a dielectric material in Flash may not be possible in device size less that about 10 nm. A new category of devices using an interconnected crossbar configuration that are vertically integrated in a three dimensional manner can have a high device density not achievable in current memory devices.
However, leakage current from a cell in an interconnected crossbar array can form a sneak path in the array. A sneak path is a current path for leakage current from one cell to propagate in an array of cells. The leakage current can interfere with proper operations (read write, or erase) in all the cells in the sneak path. To suppress the leakage current and to isolate a cell from the leakage current, a rectifier can be used. The rectifier adds complexity to the device design and could be difficult to integrate in a crossbar array. Certain devices may have rectifying behavior but such devices usually have a symmetrical IV characteristic, which does not work well in a crossbar array. Other cells may have a low on state current and thus have poor data retention properties.
Additionally, to exploit the advantage for vertically stacking of cells, controlling CMOS devices are usually first formed on a substrate and the memory arrays are subsequently fabricated above the CMOS devices. Processing temperature of the memory cells should not be greater than 500 Degree Celsius to ensure proper functioning of the CMOS devices. Embodiments of the present invention provide a device structure and related methods to form a resistive switching device that is rectifying and processing parameters that are compatible with current CMOS device processing technologies.
Referring to FIG. 1. A resistive switching device structure 100 according to an embodiment of the present invention is provided. The device structure includes a first electrode 102, a second electrode 104, and a switching material stack 110 disposed in between the first electrode and the second electrode. The switching material stack includes a first resistive switching material 106 overlying a second resistive switching material 108. In a specific embodiment, the first electrode can be a semiconductor material having a suitable electrical conducting property. For example, the first electrode may include a conductive silicon-bearing material, such as doped (e.g. P-type) polysilicon material, a doped silicon-containing layer, a doped silicon germanium material, and the like. The first electrode can also be a first metal material such as those commonly used in CMOS processing, a combination of metal and doped silicon-containing material, or the like. Examples of the first metal material are copper, tungsten, or aluminum, and other suitable metal materials. Depending on the application, the second electrode 104 has at least a portion that includes a metal material in direct contact with the first switching material. In a specific embodiment, the metal material can be silver, gold, platinum, palladium, nickel, aluminum, and others. The metal material has a desirable characteristic in the first switching material and the second switching material, for example, diffusion, oxidation and reduction, and others. In a specific embodiment, the first switching material is configured to determine a switching characteristic and retention characteristic of the resistive switching device and the second switching material is configured to control leakage current in the resistive switching device.
In a specific embodiment, the first switching material can be an amorphous semiconductor and/or sub-oxide material such as Si, Ge, SixGey, SiOx and SixGeyOz. It should be understood that any such sub-oxide refers to a non-stoichiometric oxide, as detailed in the applications incorporated by reference, above. An example of this is silicon oxide: stoichiometric silicon oxide is SiO2, and non-stoichiometric oxide may be SiOx where 0<x<2. In various embodiments, other forms of non-stoichiometric oxide may be formed or grown using various fabrication techniques. The amorphous material and/or suboxide is characterized by a switching voltage ranging from about 1.0 to about 4 volts, 1.5 volts to about 4 volts, or the like, depending on the process condition. As merely an example, the second switching material can be a solid electrolyte material. The solid electrolyte material can include be chalcogenide based such as GexSy, GexSey, SbxTey, AgxSey, and CuxSy, or can be metal oxide based such as WON, TiOx, AlOx, HfOx, CuOx, and TaOx, where 0<x<appropriate stoichiometric value (e.g. 2, 3, etc.) (e.g. GeS, GeSe, WO3, or SbTe, and the like). The solid electrolyte material can have a first switching voltage ranging from about 0.1 volt to about 1.0, about 0.1 volt to about 0.5 volt, or the like depending on the solid electrolyte material. The solid electrolyte material further provides a temperature advantage in processing, as the deposition temperature is generally less than about 400 Degree Celsius. For example, GexSy, GexSey (e.g. GeS, GeSe) and SbxSey (e.g. SbSe) can be deposited using a sputtering process performed at about room temperature. WOx (e.g. WO3) can be formed by oxidation of tungsten metal, a common material used in COMS processing, at a temperature of about 400 Degree Celsius or less. TiOx, AlOx, and HfOx can be deposited using a sputtering or an ALD (atomic layer deposition) process at lower than 400 Degree Celsius. As metal material such as copper or silver has a high diffusivity in the solid electrolyte material, the first switching voltage is small and write voltage is generally lower than erase voltage for the solid electrolyte material (for example, GexSey (e.g. GeSe) has a write voltage of about 0.4 volt and an erase voltage of about −0.2 volt). In various embodiments, an additional barrier material layer may be disposed between first switching material 106 and metal material 104. This barrier material layer may provide a barrier against undesired contaminants from affecting first switching material 106, or the like. In some embodiments, the barrier material may include titanium, titanium oxide, tungsten, or the like. Further details are given in the patent applications incorporated by reference, mentioned above.
FIG. 2 illustrates switching characteristic of the first switching device using amorphous silicon material as the switching material. The first switching device includes a first electrode 202, a second electrode 204, and an amorphous silicon material 206 disposed in between the first electrode and the second electrode. The second electrode has at least a portion that includes a metal material in a specific embodiment. The metal material can be silver, gold, platinum, palladium, nickel, aluminum, and others. As shown, when a positive voltage 208 greater than a first threshold voltage is applied to the second electrode of an as fabricated device, a metal region 210 is formed in a portion of the amorphous silicon material and causes the first switching device to be in a high resistance state or an off state. The formation of the metal region in the amorphous silicon material is a diffusion process assisted by an electric field upon application of the positive voltage to the second electrode. The metal region includes a first filament structure 212, which expands or retracts depending on an amplitude and polarity of voltage applied. To write into the switching device, a write voltage +Vth1.1 is applied, causing the first filament structure to extend. The amorphous silicon material is in a low resistance state and the first switching device is at an on state and an on state current flows in the amorphous silicon material. In various embodiments, the write voltage is a positive voltage applied to the second electrode and can range from about 1 to 6 volts depending on the process conditions of the amorphous silicon material, among others. For a switching device using only amorphous silicon material as switching material, rectification is possible for a low on state current (for example, less than about 2 u amp). However, in some configurations, filament structure is not stable at low on state current, and data retention is therefore poor.
FIG. 2A illustrates switching behavior of the first switching device using amorphous silicon material as the switching material. As shown, the first switching device has a first forward switching threshold or a first write voltage of Vth1.1 and a first erase voltage of −Vth1.2 and Vth1.1>>|Vth1.2|, that is the first erase voltage is lower that the first write voltage in absolute terms.
As shown in a simplified diagram in FIG. 3, switching behavior of a second switching device 300 using a solid electrolyte 302 as a switching material is illustrated. The second switching device includes a first electrode 306 and a second electrode 308. As shown, when a positive voltage 304 is applied to second electrode 308, a second filament structure 310 is formed in the solid electrolyte material. The second filament structure may be formed by a chemical reaction, for example, a reduction/oxidation reaction when the positive voltage is applied. The second filament structure forms a conductive path in the solid electrolyte material and causes a second low resistance state in the solid electrode material. A negative voltage applied to the second electrode would break or cause discontinuity in the second filament structure and the solid electrolyte material reverts back to a high resistive state.
FIG. 3A illustrates a switching behavior of the second switching device using solid electrolyte material as the switching material. The second switching device has a second forward switching threshold or a second write voltage of Vth2.1 and a second erase voltage of −Vth2.2 and Vth2.1>>|Vth2.21, that is the second erase voltage is lower that the second write voltage in absolute terms
In addition, |Vth1.x|>>|Vth2.x|, where x=1 or 2, that is operating voltages (write, erase or read) of the first switching device (using amorphous silicon as switching material) is configured to be greater than operating voltages of the second switching device using solid electrolyte material as switching device.
FIG. 4-8 illustrate operations of a switching device comprising two switching materials according to an embodiment of the present invention. As shown, an as fabricated device 400 is provided. The as fabricated device includes a first electrode 402, a switching material stack comprises of a first switching material 404 and a second switching material 406. The first switching material overlies the second switching material, and a second electrode 408 overlies the first switching material, as shown. In a specific embodiment, the first electrode can include a first metal material. The first metal material can be tungsten, copper, or aluminum or a conductor material commonly used in CMOS processing depending on the application. The first switching material includes an amorphous silicon material and the second switching material includes a solid electrolyte in a specific embodiment. The second electrode has at least a portion that includes a metal material in direct contact with the first switching material. In a specific embodiment, the metal material can be silver, copper, nickel, gold, palladium, aluminum or other suitable metals having a desirable diffusivity characteristic in the first switching material and the second material in a specific embodiment.
Referring again to FIG. 4, when a voltage greater than a first threshold voltage Vth1.0 for the amorphous silicon material is applied, a first metal region 410 is formed in a portion of the solid electrolyte material and a second metal region 412 is formed in a portion of the amorphous silicon material. First metal region 410 is characterized by a first filament structure and a first length. The first filament structure includes a series of metal particles to provide a conductive path in the solid electrolyte material. In a specific embodiment, second metal region 412 further includes a second filament structure characterized by a second length. In a specific embodiment, the first length and the second length depend on an operating voltage and respective switching voltage of each of the amorphous silicon material and the solid electrolyte material. The switching device is now at an initial off state in which the amorphous silicon material is in a first high resistance state and a first off state. The solid electrolyte material is in a second high resistance state or a second off state.
To write into the switching device, a second voltage greater than about a write voltage Vth1.1 for the amorphous silicon material is applied. The second filament structure in the amorphous silicon material extends 502. As the write voltage for the solid electrolyte material is lower, the second voltage would turn on both amorphous silicon material and the solid electrolyte and a third filament structure 504 is formed in the solid electrolyte material as shown in FIG. 5. The switching device is now being written in which the amorphous silicon material is in a first low resistance state and a first on state and the solid electrolyte material is in a second low resistance state or a second on state. This is only a transient state during writing. A corresponding I-V representation 504 is also shown in FIG. 5.
FIG. 6 is a simplified diagram illustrating a first erase cycle after writing when a fourth voltage more negative than a first erase voltage for the solid electrolyte material −Vth2.2 is applied. Corresponding I-V curve 604 is also shown. The third filament structure in the solid electrolyte material retracts and the solid electrolyte is back to the high resistance state. The fourth voltage is not high enough to cause the amorphous silicon to be in a low resistance state and the second filament structure 608 remains extended in the amorphous silicon material. In this instant, the amorphous silicon is in the on state or written state while the solid electrolyte material is in the off state or erase state and the device remains in a written state or on state.
To turn on the solid electrolyte material after it is in the off state (for example, as in FIG. 6), only a small voltage, greater than about Vth2.1 is needed to turn the solid electrolyte into a low resistance state or an on state. This is illustrated in FIG. 7. As shown, when a voltage greater than about Vth2.1 is applied, while the amorphous silicon in at a low resistant state, a voltage greater than about Vth2.1 causes the solid electrolyte material to be in a low resistant state. Now both the amorphous silicon material and the solid electrolyte material are in their respective low resistance states, the resistive switching device is now again being written.
FIGS. 8 illustrate an erase operation of the resistive switching device according to an embodiment of the present invention. The device starts at a written state as in FIG. 5. As shown in FIG. 5, both the solid electrolyte material and the amorphous silicon material are at their respective on states or low resistance states. A negative voltage having an amplitude greater than Vth1.2 would cause the first metal structure in the solid electrolyte material and the metal filament structure in the amorphous silicon material to retract. Now, both the amorphous silicon material and the sold electrolyte material are in their respective high resistance states and the resistive switching device is at an off state. Therefore, from FIGS. 4-8, in some embodiments, the amorphous silicon material is written first and can be erased after the solid electrolyte has been erased.
In a specific embodiment, a device state of the resistive switching device is determined by a state of the amorphous silicon material. That is the resistive switching device is at an on state if the amorphous silicon material is at an on state or a low resistance state. The device is in an off state if both the amorphous silicon material and the solid electrolyte material are in their respective high resistance states. During a write process, a voltage greater than +Vth1.1 would cause both the amorphous silicon material and the solid electrolyte to be in a low resistance state.
To determine a state of the device during a read process, a read voltage is applied. The read voltage can be in a range between +Vth2.1 and +Vth1.1, so that the read voltage would not turn on the amorphous silicon material if it is at a high resistance state or the device in at an off state. If the device is at an on state, the read voltage between +Vth2.1 and +Vth1.1 would merely measure the state of the device.
In one embodiment, in an ideal situation, during a write process, only the amorphous silicon material is caused to be at an on state, and during an erase cycle, only the amorphous silicon material is caused to be at an off state. However, this is not possible as the solid electrolyte has a lower on voltage and a lower off voltage than the amorphous silicon material, and would be turned on at the on voltage of the amorphous silicon material and would be turned off at the off voltage of the amorphous silicon material. Therefore, in a write cycle, a voltage greater than Vth1.1 would cause both the amorphous silicon material and the solid electrolyte material to be in their respective on states. A subsequent voltage between −Vth2.2 and −Vth1.2 would only turn off the solid electrolyte material and the device is at on state with only the amorphous silicon material being at on state.
In one embodiment, during a read process, if the device is at an on state, the amorphous silicon material is at an on state or at a low resistance state, the read voltage would only turn on the solid electrolyte material. The solid electrolyte is turned off after the read process using a voltage between −Vth2.2 and −Vth1.2. If the device is at an off state, only the solid electrolyte material would be turned on and the amorphous silicon material would remained at the off state, so that the read voltage would not turn on the amorphous silicon material and only determines the state of the device. An illustration is shown in a voltage pulse diagram in FIG. 9.
The state (on or off) of a device should not be altered by a read voltage. In cases where short voltage pulses are applied for a read process, voltage rises or falls in a short duration to reduce a pulse width. Voltage overshoot or undershoot can occur as shown in FIG. 10. If the device is at an off state, voltage overshoot may cause a write process in the amorphous silicon material if the amorphous silicon material is at an off state, a voltage undershoot could cause an erase process in the solid electrolyte material. Therefore, to use a short voltage pulse for read, a voltage greater that the on voltage for the solid electrolyte material (Vth2.1) is first applied. In some embodiments, if the device is in an on state, the device would be turned on by the on voltage for the solid electrolyte material. An erase voltage greater than the erase voltage for the solid electrolyte material is then applied. Alternatively, the read voltage pulse can have an amplitude between the write voltage of the solid electrolyte material and the write voltage of the amorphous silicon material followed by an erase voltage between the erase voltage of the amorphous silicon material and the erase voltage of the solid electrolyte material to ensure that the device state would not be altered in the read process.
In a specific embodiment, leakage current in the device can be suppressed during a read process as illustrated in the I-V characteristic in FIG. 11. For example, for an on state device, the amorphous silicon material is at an on state or low resistance state. Leakage current in the device is suppressed if the solid electrolyte material is at a high resistance state. Therefore, a read voltage between the erase voltage (−Vth1.2) of the amorphous silicon material and the write voltage of the solid electrolyte material (Vth2.1) would suppress leakage current. That is, the read voltage applied should be no greater than +Vth2.1 to prevent turning on the solid electrolyte material to cause leakage current (of the unselected cells) , and the read voltage should not be more negative than −Vth1.2 so that the on state of the amorphous silicon is maintained (of the unselected cells).
Embodiments according to the present invention further provide a method to suppress leakage current in an array, for example in an interconnected crossbar array, to prevent erroneous reading of a state of a target cell. A sneak path for leakage current can include at least three cells coupled to the target cell in the crossbar array as shown in FIG. 12. As merely an example, a first cell 1202, a second cell 1204, a third cell 1208, and a fourth cell 1206 in a crossbar array are provided. Each of the first cell, the second cell, the third cell, and the fourth cell has a two layer switching material configuration as shown in FIG. 1. The two layer switching material includes an amorphous silicon as the first switching material and a solid electrolyte as the second switching material. As merely an example, the first cell is the target cell for read. As shown, the second cell 1204 and the first cell 1202 share a common first electrode 1210, and the third cell 1208 and the fourth cell 1206 share a common second electrode 1212. The fourth cell 1206 is indirectly connected to the first cell 1202 through the second cell 1204 and the third cell 1208. To determine the state of the first cell, a forward biased voltage 1214 for read is applied on common first electrode 1210, as shown, to the first cell 1202 and a read current is measured. This would cause the second cell 1204 and the third cell 1208 to be forward biased as they are electrically connected to the first cell, the fourth cell 1206 would remain reverse bias since it is not directly connected to the first cell.
If the second cell 1204, the third cell 1208, and the fourth cell 1206 are each at on state, that is, the amorphous silicon material in all three cells are at low resistant state, the leakage current (e.g. via 1203, 1206 and 1208) would be most severe if no rectification is provided. In various embodiments, there are again two possibilities for each of the on state cells: the solid electrolyte material in each of the three cells (e.g. 1204, 1206, 1208) can be at on state or off state. For a first case where the solid electrolyte material in each of the three cells (1204, 1206, 1208) are at off state or high resistance state, if the read voltage is no greater than three times the write voltage of the solid electrolyte material, the solid electrolyte material (of cells 1204, 1206 and 1208) would not be turned on, no leakage current would be allowed to flow in the target cell. However, a read voltage should be greater than the write voltage for the solid electrolyte material to determine the state of the target cell. Accordingly, to read the state of a target cell, the read voltage should be greater than the write voltage of the solid electrolyte material of the target cell but no greater than three times the write voltage of the solid electrolyte material:

Vth2.1<V read<3 Vth2.1

As a device state (on or off) depends only on the state of the amorphous silicon material and independent of the state of the solid electrolyte material, a single voltage pulse is used to turn on or turn off the amorphous silicon material and therefore the device. Of course other variations, modifications, and alternatives exist and would be obvious to one skilled in the art.
Consider again the case where all the cells (e.g. 1204, 1206, 1208) in the sneak path (e.g via 1204, 1206, 1208) are at on state, and both the amorphous silicon material and the solid electrolyte in the cells in the sneak path are at on state or low resistance state. To prevent leakage current to affect the target cell (1202) during read, a forward read voltage (1214) greater than three times Vth2.2, or three times the erase voltage of the solid electrolyte material is first applied, the solid electrolyte material in the reversed biased cell (for example, the fourth cell 1206 in FIG. 4) in the sneak path will be erased and resistance in the reversed biased cell increases. Once the reversed biased cell is erased, the voltage drop across the reversed biased cell decreases and the solid electrolyte material in other cells in the sneak path are erased and the erase at a higher speed, in ns usually. Once the solid electrolyte material in the reversed biased cell is erased, the sneak path is blocked, as the cells are in a higher resistance state and the resistance of the target cell (1202) can be measured. As the magnitude of the erase voltage (Vth2.2) is usually smaller than the magnitude of write voltage (Vth2.1) for the solid electrolyte material, the forward biased cells (second cell 1204 and the third cell 1208) in the sneak path would not be affected.
Since the amorphous silicon material and the solid electrolyte material both have a high resistance at off state, more than one method and device structure may be used to fabricate a crossbar array of the resistive switching device having desired rectification characteristics, among others. The resistive switching materials can be formed as a part of the first electrode, or as a part of the second electrode, or as a switching element formed in an intersection region of the first electrode and the second electrode.
FIG. 13 is a simplified diagram illustrating a first device structure and a method for fabricating a resistive switching device using more than one switching materials according to an embodiment of the present invention is provided. The method includes providing a substrate 1302 having a surface region. The substrate can be a suitable semiconductor material such as single crystal silicon wafer, a silicon on insulator (commonly called SOI), or a silicon germanium material depending on the application. In a specific embodiment, the substrate can include one or more transistor device formed thereon. The one or more transistors provide control circuitry for the resistive switching device in a specific embodiment. A first dielectric material 1304 is formed overlying the surface region of the semiconductor substrate. The first dielectric material can be silicon oxide, silicon nitride, a high K dielectric material, a low K dielectric material, or a combination, depending on the application.
In a specific embodiment, the method includes depositing a first electrode material overlying the first dielectric material. The first electrode material can be tungsten, copper or aluminum and further includes one or more diffusion barrier or adhesion layer depending on the electrode material used.
In a specific embodiment, the method includes depositing a first switching material overlying the first electrode material. The first switching material is characterized by a first resistance depending on a first switching voltage applied to the device. In a specific embodiment, the first switching material can be a solid electrolyte material. The solid electrolyte material can be WO3, GeSe, GeS, SbTe, and the like. The first switching material can be deposited using a sputtering process from a suitable target material. For WO3 as the first switching material, the WO3 can be formed by oxidation of a tungsten electrode in a specific embodiment. Oxidation temperature can be at about 300 Degree Celsius or lower, compatible to CMOS processing. The solid electrolyte material has a switching voltage ranging from about 0.5 volt to about 1.5 volts depending on the material.
In a specific embodiment, a second switching material is deposited overlying the first switching material. The second switching material is characterized by a second resistance depending on a second switching voltage. The second switching material is configured to have a second switching voltage of second amplitude higher than that of the first switching material in a specific embodiment. The second switching material can be an amorphous silicon material in a specific embodiment. Depending on the process conditions, the amorphous silicon material can have a switching voltage ranging from about 1 volt to about 4 volts.
The method subjects the second switching material, the first switching material, and the first electrode material to a first pattern and etch process to form a first structure 1306. The first structure includes the second switching material 1308, the first switching material 1310, and the first electrode material 1312 and configured in an elongated shape and spatially oriented in a first direction in a specific embodiment. In a specific embodiment, a second dielectric material is formed overlying the first structure and spaces between the first structures. The second dielectric material is planarized to isolate each of the first structures in a specific embodiment. The first structure includes an exposed surface region of the second switching material in a specific embodiment
The method includes forming a second electrode material overlying the first structure. The second electrode material has a first portion 1314 that includes a metal material in a specific embodiment. The metal material is in direct contact with the second switching material in a specific embodiment. The metal material is characterized by a suitable mobility and diffusivity in the first switching material and the second switching material in a specific embodiment. The second electrode material further includes a second portion 1316 that forms a wiring structure for the resistive switching device in a specific embodiment. For amorphous silicon material as the second switching material, the metal material can include silver, gold, palladium, copper, aluminum, nickel and the likes.
In a specific embodiment, the second electrode material is subjected to a third pattern and etch process to form a second electrode structure. The second electrode structure is elongated in shape and spatially disposed in a second direction at an angle to the first direction. In a specific embodiment, the first electrode structure and the second electrode structure are orthogonal to each other to form a crossbar structure. The first switching material and the second switching material are disposed in an intersecting region formed by the first electrode structure and the second electrode structure in a specific embodiment.
Depending on the embodiment, there can be variations to the method of forming the resistive switching device as illustrated in FIG. 14. In a specific embodiment, the method includes forming a first electrode structure 1412 in a portion of the first dielectric material 304. The first electrode structure 1412 is elongated in shape and spatially extended in a first direction in a specific embodiment. The first electrode structure can be formed by first depositing an electrode material overlying the first dielectric material followed by a first pattern and etch process. The first electrode material can be tungsten, copper or aluminum and further includes one or more diffusion barrier or adhesion layer depending on the electrode material used. A second dielectric material is formed overlying the first electrode structure and filling gaps between the first electrode structures. The second dielectric material is subjected to a planarizing process to expose a surface region of the first electrode structure and to isolate the first electrode structure in a specific embodiment.
Alternatively, the first electrode structure can be formed by a damascene process. The damascene process includes formed an opening structure in the first dielectric material by a second pattern and etch process. The first electrode material including the one or more diffusion barrier or adhesion layer is formed to fill the opening structure and a thickness overlying the first dielectric material. The method then performs a planarization process to remove the first thickness of first electrode material overlying the first dielectric material to isolate the first electrode material in the opening structure in a specific embodiment. The first electrode structure is configured in an elongated manner and extends in a first direction in a specific embodiment.
In a specific embodiment, the method forms a first switching material comprising a solid electrolyte material 1410 overlying the first electrode structure and a second switching material 1408 overlying the first switching material. A metal material 1414 is formed overlying the second switching material. Similar to the device structure in FIG. 13, the first switching material 1410 comprises a solid electrolyte material and the second switching material comprises an amorphous silicon material. The metal 1414 can include silver, gold, palladium, copper, aluminum, nickel and the likes. Silver material in and the respective dielectric material depend on the way the first electrode structure is formed. The second switching material 1408 comprising an amorphous silicon material is formed overlying the first switching material. The method subjects the first switching material, the second switching material, and the metal material to a third pattern and etch process to form a plurality of pillar structures 1406. As shown, each of the pillar structures includes the first switching material, the second switching material, and the metal material in a specific embodiment. Each of the pillar structures are formed overlying at least a portion of the first electrode structure and maintain an electrical contact with the first electrode structure in a specific embodiment.
The method includes forming a third dielectric material overlying each of the pillar structures. The third dielectric material is planarized to expose a surface region of the metal material and to isolate each of the pillar structures in a specific embodiment. A second electrode material is deposited overlying the metal material and the planarized third dielectric material in a specific embodiment. The second electrode material has a first portion that include the metal material selected from silver, gold, palladium, copper, aluminum, nickel and the likes for amorphous silicon material as the second switching material. The second electrode material further includes a second portion 1416 for a second wiring structure for the switching device in a specific embodiment. The second electrode material is subjected to a fourth pattern and etch process to form a second electrode structure overlying the at least the second switching material and the third dielectric material. In a specific embodiment, the second electrode structure is configured to extend in a second direction at an angle to the first angle. In a preferred embodiment, the second electrode is configured orthogonal to the first electrode structure.
Depending on the application there can be other variations as shown in a simplified diagram in FIG. 15. Embodiment in FIG. 15 forms a first electrode structure 1512 spatially disposed in a first direction. A second structure 1506 comprising the first switching material 1508, the second switching material 1510, the metal material 1514, and the second electrode material 1516 is formed overlying at least the first electrode structure 1512. In a specific embodiment, the second structure is elongated in shape and spatially configured in a second direction orthogonal to the first direction in a specific embodiment.
Accordingly, examples in FIGS. 13, 14, and 15 illustrate ways to form a crossbar array of switching devices using more than one switching material according to embodiments of the present invention. The switching device has desirable properties to form a crossbar array of devices, for example rectifying, good retention characteristics, among others. Of course one skilled in the art would recognized other variations, modifications, and alternatives.
Though the present invention has been described using various examples and embodiments, it is also understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or alternatives in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims.

## Claims

1. A non-volatile memory device structure comprising:
a first plurality of electrodes, wherein each electrode from the first plurality of electrodes comprises a conductive silicon-containing material;
a plurality of resistive switching material stacks overlying the plurality of first electrodes, wherein each resistive switching material stack from the plurality of resistive switching material stacks comprises a first resistive switching material and a second resistive switching material, wherein the second resistive switching material overlies the first electrode, wherein the first resistive switching material overlies and contacts the second resistive switching material, wherein the first resistive switching material is characterized by a first switching voltage having a first amplitude, wherein the second resistive switching material is characterized by a second switching voltage having a second amplitude, wherein the second amplitude is less than the first amplitude;
a second plurality of electrodes, wherein each electrode from the second plurality of electrodes comprises a metal material overlying and electrically coupled to first resistive switching material of resistive switching material stacks from the plurality of resistive switching material stacks; and
wherein a plurality of memory elements are formed from the first plurality of electrodes, the plurality of resistive switching material stacks, and the second plurality of electrodes.

2. The device of claim 1 wherein a state of a memory element from the plurality of memory elements is characterized by a resistance state of a first resistive switching material of the memory element.

3. The device of claim 1
wherein the second resistive switching material is configured to suppress a leakage current through memory elements from the plurality of memory elements other than a targeted memory element, upon application of the first switching voltage across the targeted memory element.

4. The device of claim 1 wherein the second resistive switching material is configured to maintain a high resistance state until after the second switching voltage is applied, after which the second resistive switching material is configured to maintain a low resistance state.

5. The device of claim 1 wherein the first resistive switching material is characterized by a switching voltage having an amplitudes in a range selected from a group consisting: about 1 volt to about 4 volts, about 1.5 volts to about 4 volts.

6. The device of claim 1 wherein the second resistive switching material is selected from a group consisting of: a chalcogenide, a metal oxide.

7. The device of claim 1 wherein the second resistive switching material is selected from a group consisting of: GeS, GeSe, WO3, SbTe, GexSy, GexSey, SbxTey, AgxSey, CuxSy, WOx, TiOx, AlOx, HfOx, CuOx, and TaOx, where 0<x<appropriate stoichiometric value, and where 0<y<appropriate stoichiometric value.

8. The device of claim 7 wherein the second resistive switching material is characterized by a switching voltage having an amplitude in a range selected from a group consisting: about 0.1 volts to about 1 volts, about 0.1 volts to about 0.5 volts.

9. The device of claim 1 wherein the metal material is selected from a group consisting of: silver, copper, gold, platinum, palladium, aluminum, nickel.

10. The device of claim 1 wherein the first switching voltage (Vth1.1) and the second switching voltage (Vth2.1) have the following relationship: |Vth1.1|>>|Vth2.1|.

11. The device of claim 1 wherein the second switching voltage (Vth2.1) and a second reset voltage (Vth2.2) associated with the second resistive switching material have a relationship selected from a group consisting of: |Vth1.1|≠ |Vth2.1|, |Vth1.1>>|Vth2.1|.

12. The device of claim 1 wherein the first switching voltage (Vth1.1) and an erase voltage (Vth1.2) associated with the first resistive switching material have a relationship selected from a group consisting of: |Vth1.1|≠ |Vth2.1|, |Vth1.1|>>|Vth2.1|.

13. The device of claim 1 further comprising a barrier material disposed between first resistive switching material stacks from the plurality of resistive switching material stacks and the second plurality of electrodes, wherein the barrier material is selected from a group consisting of: titanium, titanium oxide, tungsten-bearing material.

14. The device of claim 13 wherein the conductive silicon-containing material is selected from a group consisting of: p-doped polysilicon, p-doped silicon and germanium containing material.

15. A method for writing to a resistive switching device, comprising:
providing a plurality of resistive switching devices, wherein the plurality of resistive switching devices comprises a first plurality of electrodes, a plurality of switching material stacks, wherein each switching material stack comprises a first switching material and a second switching material, wherein the second switching material overlies the first plurality of electrodes, wherein the first switching material overlies the second switching material, wherein a second plurality of electrodes overlies the first switching material, wherein the second plurality of electrodes comprise at least a metal material, wherein the first switching material is characterized by a first switching voltage, wherein the second switching material is characterized by a second switching voltage, wherein the first switching voltage is characterized by a first amplitude, wherein the second switching device is characterized by a second amplitude, and wherein the first amplitude is greater than the second amplitude; and
applying a first voltage across an electrode from the second plurality of electrodes and an electrode from the first plurality of electrodes thereby applying the first voltage across a switching material stack from the plurality of switching material stacks, wherein the first voltage is greater than a write voltage to thereby cause first resistive switching material of the switching material stack to change from a high resistance state to a low resistant state.

16. The method of claim 15 wherein applying the first voltage further causes the second resistive switching material of the switching material stack to change from a high resistance state to a low resistance state.

17. The method of claim 15 wherein when applying the first voltage across the electrode from the second plurality of electrodes and the electrode from the first plurality of electrodes, the first switching voltage is inhibited from being applied to switching material stacks from the plurality of switching material stacks other than the switching material stack.

18. A method for reading from a resistive switching device, comprising:
providing a plurality of resistive switching devices, wherein the plurality of resistive switching devices comprises a first plurality of electrodes, a plurality of switching material stacks, wherein each switching material stack comprises a first switching material and a second switching material, wherein the second switching material overlies the first plurality of electrodes, wherein the first switching material overlies the second switching material, wherein a second plurality of electrodes overlies the first switching material, wherein the second plurality of electrodes comprise at least a metal material, wherein the first switching material is characterized by a first switching voltage, wherein the second switching material is characterized by a second switching voltage, wherein the first switching voltage is characterized by a first amplitude, wherein the second switching device is characterized by a second amplitude, and wherein the first amplitude is greater than the second amplitude; and
applying a first voltage across an electrode from the second plurality of electrodes and an electrode from the first plurality of electrodes thereby applying the first voltage across a switching material stack from the plurality of switching material stacks, wherein the first voltage is greater than the second switching voltage but lesser than a write voltage of the first switching material to thereby cause second resistive switching material of the switching material stack to change from a high resistance state to a low resistance state.

19. The method of claim 18 wherein when applying the first voltage across the electrode from the second plurality of electrodes and the electrode from the first plurality of electrodes, the second switching voltage is inhibited from being applied to switching material stacks from the plurality of switching material stacks other than the switching material stack.

20. The method of claim 18 wherein when applying the first voltage across the electrode from the second plurality of electrodes and the electrode from the first plurality of electrodes, switching material stacks from the plurality of switching material stacks other than the switching material stack remain in a high resistance state.