# Patent

## Title
Resistive switching device structure with improved data retention for non-volatile memory device and method

## Abstract

A non-volatile memory device structure includes a first conductor extending in a first direction, a second conductor extending in a second direction approximately orthogonal to the first direction, an amorphous silicon material disposed in an intersection between the first and second conductors characterized by a first resistance upon application of a first voltage, wherein the first resistance is dependent on a conductor structure comprising material from the second conductor formed in a portion of the resistive switching material, and a layer of material configured in between the second conductor and the amorphous silicon material, wherein the layer maintains at least a portion the conductor structure in the amorphous silicon material, and wherein the layer inhibits conductor species from the portion of the conductor structure from migrating away from the second conductor when a second voltage having an amplitude less than the first voltage is applied.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
Not Applicable
STATEMENTS RELATED TO GOVERNMENT OR FEDERALLY FUNDED RESEARCH
Not Applicable
BACKGROUND
The inventor of the present invention has recognized the success of semiconductor devices has been mainly driven by an intensive transistor down-scaling process. However, as field effect transistors (FETs) approach sizes less than 100 nm, physical problems such as short channel effect begin to hinder proper device operation. For transistor based memories, such as those commonly known as Flash memories, other performance degradations or problems may occur as device sizes shrink. With Flash memories, a high voltage is usually required for programming of such memories, however, as device sizes shrink, the high programming voltage can result in dielectric breakdown and other problems. Similar problems can occur with other types of non-volatile memory devices other than Flash memories.
The inventor of the present invention recognizes that many other types of non-volatile random access memory (RAM) devices have been explored as next generation memory devices, such as: ferroelectric RAM (Fe RAM); magneto-resistive RAM (MRAM); organic RAM (ORAM); phase change RAM (PCRAM); and others.
A common drawback with these memory devices include that they often require new materials that are incompatible with typical CMOS manufacturing. As an example of this, Organic RAM or ORAM requires organic chemicals that are currently incompatible with large volume silicon-based fabrication techniques and foundries. As another example of this, Fe-RAM and MRAM devices typically require materials using a high temperature anneal step, and thus such devices cannot be normally be incorporated with large volume silicon-based fabrication techniques.
Additional drawbacks with these devices include that such memory cells often lack one or more key attributes required of non-volatile memories. As an example of this, Fe-RAM and MRAM devices typically have fast switching (e.g. “0” to “1”) characteristics and good programming endurance, however, such memory cells are difficult to scale to small sizes. In another example of this, for ORAM devices reliability of such memories is often poor. As yet another example of this, switching of PCRAM devices typically includes Joules heating and undesirably require high power consumption.
From the above, improved semiconductor memory devices that can scale to smaller dimensions with reduced drawbacks are therefore desirable.
BRIEF SUMMARY OF THE PRESENT INVENTION
The present invention is generally related to resistive switching devices. More particularly, embodiments according to the present invention provide a device structure and a method to improve device performance of a resistive switching device. The present invention can be applied to non-volatile memory devices but it should be recognized that the present invention can have a much broader range of applicability.
The terms “bottom” and “top” are for purpose of illustration and reference only, and should not be limiting.
In a specific embodiment, a non-volatile memory device is provided. The device includes a bottom electrode, a top electrode, a resistive switching material disposed in an intersecting region of the first electrode and the bottom electrode. The first electrode comprises a first conductor material, the top electrode comprises a second conductor material and the resistive switching material comprises a silicon material (for example, an amorphous silicon material) in a specific embodiment. The resistive switching material is characterized by at least a first resistance upon application of a first voltage. In a specific embodiment, the first resistance is dependent on at least a first portion of a conductor structure comprising the second conductor material formed in a portion of the resistive switching material. In a specific embodiment, the device includes a layer of material configured between the bottom electrode and the resistive switching material. The layer of material is configured to maintain at least the first portion the first conductor structure in the portion of the resistive switching material and acts as a barrier region to maintain conductor species from the first conductor structure from migrating to another portion of the resistive switching material when a second voltage having an amplitude less than the first voltage is applied. The second voltage can be, for example, a read voltage for the non-volatile memory device.
According to one aspect of the invention, a non-volatile memory device is disclosed. According to one aspect of the invention, a non-volatile memory device structure is disclosed. One device includes a bottom electrode comprising a first conductor material extending in a first direction, and a top electrode comprising a second conductor material extending in a second direction, the first direction being approximately orthogonal to the second direction. One device includes a resistive switching material comprising an amorphous silicon-containing material disposed in an intersection region between the bottom electrode and the top electrode, the resistive switching material being characterized by at least a first resistance upon application of a first voltage, the first resistance being dependent on at least a first portion of a conductor structure comprising the second conductor material formed in a portion of the resistive switching material, and a layer of material configured in between the bottom electrode and the resistive switching material, the layer of material being configured to maintain at least the first portion the conductor structure in the portion of the resistive switching material, the layer of material acting as a barrier region to inhibit conductor species from the conductor structure from migrating away from the bottom electrode when a second voltage having an amplitude less than the first voltage is applied.
According to another aspect of the invention, a non-volatile memory device structure is described. One device includes a bottom electrode comprising a metal material extending in a first direction, a contact layer comprising a doped silicon-containing material disposed above the bottom electrode, and a top electrode comprising a metal material extending in a second direction, the first direction being approximately orthogonal to the second direction. One device includes a resistive switching material comprising an amorphous silicon-containing material disposed above the contact layer and disposed in an intersection region between the bottom electrode and the top electrode, wherein the resistive switching material is characterized by at least a first resistance upon application of a first voltage across the top electrode and bottom electrode, wherein the first resistance is dependent on at least a first portion of a conductor structure formed in a portion of the resistive switching material, and wherein the conductor structure is formed from the metal material of the top electrode, and a layer of material disposed above the contact layer and below the resistive switching material, wherein the layer of material is configured to inhibit conductor species from the conductor structure from migrating away from the bottom electrode when a second voltage having an amplitude less than the first voltage is applied across the top electrode and the bottom electrode.
Many benefits can be achieved by ways of the present invention. Embodiments of the present invention provide a device structure and a method to maintain a predetermined resistance state of the resistive switching device and to improve data retention characteristic of the device. The present device can be fabricated using conventional process techniques without modification to the process equipment. Depending upon the embodiment, one or more of these benefits may be achieved. One skilled in the art would recognize other modifications, variations, and alternatives.



SUMMARY OF THE DRAWINGS
In order to more fully understand the present invention, reference is made to the accompanying drawings. Understanding that these drawings are not to be considered limitations in the scope of the invention, the presently described embodiments and the presently understood best mode of the invention are described with additional detail through use of the accompanying drawings in which:
FIGS. 1 and 2 are simplified diagrams illustrating a resistive switching device according to an embodiment of the present invention;
FIGS. 3-5 are simplified diagrams illustrating operations of a resistive switching device according to an embodiment of the present invention;
FIG. 6 is a simplified diagram illustrating a device structure for a resistive switching device according to an embodiment of the present invention;
FIGS. 7-9 are simplified energy level diagrams for the resistive switching device according to an embodiment of the present invention; and
FIGS. 10-11 are simplified energy level diagrams for the resistive switching device under small bias conditions according to an embodiment of the present invention.



DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention is generally related to resistive switching devices. More particularly, embodiments according to the present invention provide a device structure and a method to improve device performance of a resistive switching device The present invention can be applied to improving data retention characteristic of non-volatile memory devices, but it should be recognized that embodiments according to the present invention can have a much broader range of applicability
Some embodiments of a resistive switching device include a two terminal device including a top electrode, a bottom electrode and a resistive switching material disposed between the top electrode and the bottom electrode. The resistive switching material is characterized by a resistance dependent on an electric field upon an application of a suitable voltage to one of the electrodes. The electric field causes a conductor path to form in the resistive switching material. Depending on the electrode material and the resistive switching material used, the conductor path can be formed from the electrode material or defect path in the presence of the electric field. The conductor path determines the resistance of the resistive switching material. For example, for a metal oxide material as the switching material, the conductor path can form from oxygen deficient sites in the metal oxide. For a silicon material as the switching material, the conductor path can be formed from the electrode material, which comprises an active metal material. The resistive switching material is in a high conductance state. The conductor path is broken or retracts when a reverse bias voltage is applied and causes the resistive switching material to be in a low conductance state. The resistance of the resistive switching material has a resistance depending on the voltage and provide for a multi-level or multi-bit device. Therefore the conductor path structure needs to be stable under selected voltage, forward bias voltage, or reverse bias voltage for proper data retention.
Embodiments according to the present invention provide a device structure and a method for a resistive switching device characterized by a stable conductive path when a predetermined voltage is applied and a reliable data retention characteristic for the device.
FIG. 1 is a simplified diagram illustrating a resistive switching device 100 according to an embodiment of the present invention. The resistive switching device includes a first electrode 102, a second electrode 106, and a resistive switching material 104 sandwiched between the first electrode and the second electrode.
In various embodiments, resistive switching device 100 is formed upon a semiconductor substrate (not shown). In certain embodiments, the semiconductor substrate can have one or more MOS devices formed thereon. The one or more MOS devices can be controlling circuitry for the resistive memory devices in specific embodiments. In other embodiments, the one or more MOS devices may include other functionality, such as a processor, logic, or the like.
In various embodiments, a processor, or the like, may include resistive memory memories as described herein. Because the resistive state-change memories are relatively non-volatile, the states of devices, such as processors, or the like may be maintained while power is not supplied to the processors. To a user, such capability would greatly enhance the power-on power-off performance of devices including such processors. Additionally, such capability would greatly reduce the power consumption of devices including such processors. In particular, because such resistive memories are non-volatile, the processor need not draw power to refresh the memory states, as is common with CMOS type memories. Accordingly, embodiments of the present invention are directed towards processors or other logic incorporating these memory devices, as described herein, devices (e.g. smart phones, network devices) incorporating such memory devices, and the like.
In various embodiments, in FIG. 2, the first electrode 102 can be a first conductor material. The first electrode 102 can include a first conductive material such as a first metal material and/or a doped semiconductor material 112. In a specific embodiment, the first metal material 102 can be tungsten, aluminum, copper or other suitable metal that are compatible with CMOS fabrication techniques. In additional embodiments, a doped semiconductor material 112 may be p-doped polysilicon, p-doped silicon germanium, or the like. In a specific embodiment, the first electrode is elongated in shape and configured to extend in a first direction 108.
The resistive switching material 104 can include a suitable insulator material having a resistance that can be altered upon application of an electric field to the insulator material. In a specific embodiment, the resistive switching material 104 can include a silicon material. For example, the silicon material can be an amorphous silicon material, a microcrystalline silicon material, a macro crystalline silicon material, a silicon germanium material including any combination of these. In a preferred embodiment, the silicon material includes an amorphous silicon material.
The resistive switching material 104 is characterized by a state, for example, a resistance state dependent on an electric field in the switching material. In a specific embodiment, the switching material is an amorphous silicon material. The amorphous silicon material has essentially intrinsic semiconductor characteristic and is not intentionally doped in a specific embodiment. In various embodiments, the amorphous silicon is also referred to as non-crystalline silicon (nc-Si). nc-Si non-volatile resistive switching devices may be fabricated using existing CMOS technologies. In an exemplary process, a mixture of silane (SiH4)(45 sccm) and Helium (He) (500 sccm) is used to form an a-Si layer with a deposition rate of 80 nm per minute (T=260° C., P=600 mTorr) during PECVD. In another exemplary process, a mixture of silane (SiH4)(190 sccm) and Helium (He) (100 sccm) is used to form an a-Si layer with a deposition rate of 2.8 A per second (T=380° C., P=2.2 Torr) during PECVD. In another exemplary process, silane (SiH4 80 sccm) or disilane is used to form an a-Si layer with a deposition rate of 2.8 nm per minute (T=585° C., P=100 mTorr) during LPCVD. Portions of poly-silicon grains may form during the LPCVD process and result in an amorphous-poly silicon film. In various embodiments, no p-type, n-type, or metallic impurities are intentionally added to the deposition chamber while forming the amorphous silicon material. Accordingly, when deposited, the amorphous silicon material is substantially free of any p-type, n-type or metallic dopants, i.e. the amorphous silicon material is undoped.
In yet another embodiment, the resistive switching material/amorphous silicon material 104 may be formed from an upper region of a p+ polycrystalline silicon or p+ silicon germanium bearing layer (e.g. 112) using an Argon, Silicon, Oxygen plasma etch, or the like. For instance, a plasma etch may use a bias power within a range of approximately 30 watts to approximately 120 watts to convert an upper region of the polysilicon or silicon germanium material into a non-conductive amorphous silicon having p-type impurities (from the original polycrystalline silicon or silicon germanium bearing layer 112).
The second electrode 106 can be a second conductor material and can have a portion that includes a second metal material. The second metal material can be selected from aluminum, nickel, silver, gold, palladium, platinum, and others. The second metal material may have a suitable diffusivity in the switching material in a specific embodiment. In a specific embodiment, the second electrode is elongated in shape and configured to extend in a second direction 110 orthogonal to the first direction 108. In a specific embodiment, the second metal material includes a silver material.
As mentioned above, in certain embodiments, the resistive switching device 100 can include a contact material (112) disposed between the metal material of the first electrode 102 and the amorphous silicon material 104. In some embodiments, the contact material 112 provides a suitable interfacial defect characteristic for desirable switching behavior for the switching device 100. For amorphous silicon material as the switching material 104, the contact material 112 can be p+ polysilicon or p+ silicon germanium material. In certain embodiments, the contact material 112 can be optional.
In various embodiments, additional interposing layer(s) 114 may be disposed between resistive switching material 104 and second electrode 106. The additional layer 114 may include a material that has non-noble metal properties, e.g. the material oxidizes in the presence of oxygen. In some examples, the additional layer 114 may be titanium, titanium nitride, tungsten, tungsten nitride, or the like. In various embodiments, additional layer 114 may serve as an adhesion and/or bather layer between resistive switching material 104 and second electrode 106. In various embodiments, additional layer(s) 114 may be used to enhance retention, as will be described below.
In various embodiments, multiple resistive switching devices 100 can be disposed in an N by M crossbar array to form a high density interconnected array of non-volatile memory cells.
FIGS. 3-5 are simplified diagrams illustrating operations of the resistive switching device. As shown in FIG. 3, the second metal material 106 forms a metal region 302 in a portion of the switching material when a first positive voltage 304 greater than a threshold voltage is applied to the second electrode. The threshold voltage is the forming voltage for the resistive switching device.
As illustrated in FIG. 4, when a second positive bias voltage 406 (e.g. a write voltage) is applied to the second electrode 106, a filament region 402 is formed. Filament region 402 is typically characterized by a length, a first distance between metal particles, and/or a second distance between the filament and the first electrode 102. As shown in FIG. 4, the filament extends 404 towards the first electrode 102. In this configuration, the resistive switching device is now at a low resistance state.
In FIG. 5, the filament structure retracts 502 when a negative bias voltage 504 (e.g. an erase voltage) is applied to the second electrode 106 after the configuration illustrated in FIG. 4. In various embodiments, the resistive switching device is reverted back to a high resistance state. Accordingly, in some examples, the resistive switching device is a two-terminal device or a bipolar device.
Referring again to FIG. 4, the resistance state of the device is determined at least by the length of the filament structure, the distance between the metal particles in the filament structure, and the distance between the filament structure and the bottom electrode. As shown, the on-state current is determined by a tunneling current from the metal particle in the filament structure 402. As the device is cycled through read, write, and erase cycles, the filament structure may not maintain its desired structure. Additionally, in some embodiments, temperature effects resulting from current flows through the device, as well as from the ambience further degrade the filament structure. Degradation of the filament structure affects data retention characteristic for the device.
FIG. 6 illustrates a device structure 600 for improving data retention for a resistive switching device according to some embodiments of the present invention. As shown, the device structure further includes a tunneling barrier layer 602 disposed in a portion of the resistive switching material between resistive switching material 104 and bottom electrode 102. For amorphous silicon as the resistive switching material 104, the tunneling layer 602 can alternatively be disposed sandwiched between a p+ polysilicon contact material 112 and bottom electrode 102 or between p+ polysilicon contact material 112 and resistive switching material 104 in some embodiments.
FIGS. 7-9 are simplified energy diagrams of the resistive switching device under conditions of no bias (or slight bias), forward bias, and reverse bias. As shown in FIG. 7, the tunneling barrier layer 602 is characterized by an energy band 702 having a barrier width 712. As shown, the bottom electrode 102 is at a first energy level 704 and the top electrode 106 is at a second energy level 708. The p+ polysilicon material 112 has a third energy level 706 and the amorphous silicon material 104 has a fourth energy level 710.
In operation, when a positive voltage is applied to the top electrode 106, the energy band 702 of the tunneling barrier layer 602 is extended and the barrier width is reduced, as illustrated in FIG. 8. Accordingly, the energy band is configured to facilitate or allow conductive particles 804 to tunnel through in a first direction 802 under a forward bias voltage. This causes the device to be at an ON state or a programmed state. The device is characterized by a low resistance state and an ON state current flows in the device.
Subsequently, when a small bias (forward or reversed) is applied to the device, for example in a read operation, or under no bias condition (as in FIG. 7), as illustrated in FIG. 9, conductive particles 804 that have tunneled through the tunneling barrier 602 now experience a large barrier 1002 in addition to the resistive switching material. Accordingly, conductive particles 804 are maintained in contact with tunneling barrier 602, and the device remains at a low resistance state.
In FIG. 10, the energy band of the tunneling barrier layer 602 is further configured to allow conductive particles 804 to tunnel through in a second direction (back towards second conductor 106) under a reverse bias voltage (for example, an erase voltage). Accordingly, conductive particles 804 retract and the device is in a high resistance state as shown in FIG. 11.
Once retracted, the small bias voltage for read operation is again not large enough for the conductive particles 804 to tunnel through the tunnel barrier layer 602 to cause the device to go into a low resistance, programmed state. Accordingly, the tunnel barrier layer 602 is configured to maintain a resistance state of a resistance switching device under no bias or small bias condition.
Depending on the embodiment, the tunneling barrier layer 602 can have a suitable thickness, a suitable dielectric constant, or combination thereof. In some embodiments, the tunneling barrier layer 602 can have a thickness within a range of about 40 nm to about 50 nm depending on the dielectric constant; in some embodiments, tunneling barrier layer 602 can have a thickness of within a range of about 30 nm to about 20 nm; and in some embodiments, tunneling barrier layer 602 can have a thickness of within a range of about 10 nm to about 20 nm. The typical thickness is much larger than any incidental and unintentional native oxides, if any, that may form above any contact material 112.
Additionally, the tunneling barrier layer 602 is selected to be compatible with the resistive switching material 104 and the bottom electrode 102 in a specific embodiment. The tunneling barrier layer can be a dielectric material, or a semiconductor material, or a metal, including any combinations of these and others. In some embodiments, the tunneling barrier layer 602 may be a silicon nitride, a silicon oxide, titanium oxide, zinc oxide, or the like. In view of the present disclosure, one of ordinary skill in the art will recognize that many other materials that may be used for tunneling barrier layer 602.
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 bottom electrode comprising a first conductor material extending in a first direction;
a top electrode comprising a second conductor material extending in a second direction, the first direction being approximately orthogonal to the second direction;
a resistive switching material comprising an amorphous silicon-containing material disposed in an intersection region between the bottom electrode and the top electrode, the resistive switching material being characterized by at least a first resistance upon application of a first voltage, the first resistance being dependent on at least a first portion of a conductor structure comprising the second conductor material formed in a portion of the resistive switching material; and
a layer of material configured in between the bottom electrode and the resistive switching material, the layer of material being configured to maintain at least the first portion the conductor structure in the portion of the resistive switching material, the layer of material acting as a tunneling barrier region configured to allow conductor species from the conductor to tunnel to the bottom electrode when the first voltage is applied and configured to inhibit conductor species from the conductor structure from migrating away from the bottom electrode when a second voltage having an amplitude less than the first voltage is applied.

2. The device of claim 1 wherein the first portion of the conductor structure is characterized by a filament structure having a length and a distance between conductor particles, the filament structure extending in a direction from the top electrode towards the bottom electrode upon application of the first voltage.

3. The device of claim 1 wherein the layer of material is selected from a group consisting of: a dielectric material, a semiconductor material, a metal oxide.

4. The device of claim 1 wherein the layer of material is further configured to allow the first portion of the conductor structure to retract upon application of a reversed bias voltage having an amplitude greater than the programming voltage and a polarity opposite to the programming voltage.

5. The device of claim 1 wherein the amorphous silicon-bearing material is selected from a group consisting of: an amorphous silicon, a microcrystalline silicon material, a silicon oxide, a silicon germanium material, and combinations thereof.

6. The device of claim 1 wherein the bottom electrode also comprises a contact layer comprising a material, wherein the material is selected from a group consisting of: doped polysilicon, and doped silicon germanium.

7. The device of claim 1 wherein the second conductor material is selected from a group consisting of: a noble metal, gold, platinum, silver, palladium, nickel, or aluminum.

8. The device of claim 1 wherein the layer of material is configured to provide a first tunneling threshold when a programming or erase voltage is not applied across the top electrode and the bottom threshold, and configured to provide a second tunneling threshold when the programming or the erase voltage is applied across the top electrode and the bottom threshold, and wherein the first tunneling threshold is greater than the second tunneling threshold.

9. The device of claim 8 wherein the second tunneling threshold is approximately half the first tunneling threshold.

10. The device of claim 1 wherein the layer of material has a thickness within a range of approximately 10 nm to approximately 50 nm.

11. A non-volatile memory device structure comprising:
a bottom electrode comprising a metal material extending in a first direction;
a contact layer comprising a doped silicon-containing material disposed above the bottom electrode;
a top electrode comprising a metal material extending in a second direction, the first direction being approximately orthogonal to the second direction;
a resistive switching material comprising an amorphous silicon-containing material disposed above the contact layer and disposed in an intersection region between the bottom electrode and the top electrode, wherein the resistive switching material is characterized by at least a first resistance upon application of a first voltage across the top electrode and bottom electrode, wherein the first resistance is dependent on at least a first portion of a conductor structure formed in a portion of the resistive switching material, and wherein the conductor structure is formed from the metal material of the top electrode; and
a layer of material disposed above the contact layer and below the resistive switching material, wherein the layer of material is configured to allow conductor species from the conductor to tunnel to the bottom electrode when the first voltage is applied and configured to inhibit conductor species from the conductor structure from migrating away from the bottom electrode when a second voltage having an amplitude less than the first voltage is applied across the top electrode and the bottom electrode.

12. The device of claim 11 wherein material from the layer of material is selected from a group consisting of: a dielectric material, a semiconductor material, a metal oxide, a metal material, a silicon nitride, a silicon oxide, titanium oxide, zinc oxide.

13. The device of claim 11
wherein the layer of material is configured to inhibit conductor species from the conductor structure from migrating away from the bottom electrode when a second voltage having an amplitude less than the first voltage is applied across the top electrode and the bottom electrode to a first degree;
wherein the layer of material is configured to inhibit conductor species from the conductor structure from migrating away from the bottom electrode when a second voltage having an amplitude approximately equal to the first voltage is applied across the top electrode and the bottom electrode to a second degree; and
wherein the first degree is greater than the second degree.

14. The device of claim 11 wherein the amorphous silicon-bearing material is selected from a group consisting of: an amorphous silicon, a microcrystalline silicon material, a silicon oxide, a silicon germanium material, and combinations thereof.

15. The device of claim 11 wherein the doped silicon-containing material is selected from a group consisting of: doped polysilicon, and doped silicon germanium.

16. The device of claim 11 wherein the second conductor material is selected from a group consisting of: a noble metal, gold, platinum, silver, palladium, nickel, or aluminum.

17. The device of claim 11 wherein the second conductor material comprises aluminum.

18. The device of claim 11 wherein the layer of material is configured to provide a first tunneling threshold when a programming or erase voltage is not applied across the top electrode and the bottom threshold, and configured to provide a second tunneling threshold when the programming or the erase voltage is applied across the top electrode and the bottom threshold, and wherein the first tunneling threshold is greater than the second tunneling threshold.

19. The device of claim 18 wherein the second tunneling threshold is approximately half the first tunneling threshold.

20. The device of claim 11 wherein the layer of material has a thickness within a range of approximately 20 nm to approximately 40 nm.