# Patent

## Title
Resistive memory device and fabrication methods

## Abstract

A method for forming a resistive memory device includes providing a substrate comprising a first metal material, forming a conductive silicon-bearing layer on top of the first metal material, wherein the conductive silicon-bearing layer comprises an upper region and a lower region, and wherein the lower region is adjacent to the first metal material, forming an amorphous layer from the upper region of the conductive silicon-bearing layer, and disposing an active metal material above the amorphous layer.

## Background
CROSS-REFERENCE TO RELATED CASES
The present invention claims priority to and is a non-provisional of Ser. No. 61/620,561 filed Apr. 5, 2012. That application is herein by incorporated by reference for all purposes.


BACKGROUND
The present invention relates to memory devices. More particularly, the present invention discloses non-volatile resistive switch memory devices having improved operational characteristics, fabrication techniques, as well as apparatus including such memories.
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 relates to memory devices. More particularly, embodiments according to the present invention disclose memory (e.g. switching) devices having improved data retention characteristics and methods for forming such devices. Embodiments are described with respect to non-volatile memory devices, however, embodiments may also be applied to a broader range of memory devices, processing devices, and the like.
Various processes include fabrication of a resistive memory device. One process includes forming a conductive silicon layer, such as a p-doped polysilicon or silicon/germanium alloy, in electrical contact and above a first metal layer (e.g. aluminum). The conductive silicon layer is then subject to a plasma etch or ion implantation step (e.g. Argon, Oxygen, Silicon), that changes an upper region of the conductive silicon layer into an amorphous layer. The non-conductive amorphous layer may include oxygen, non-crystalline silicon, silicon dioxide, and p-type impurities, but is relatively non-conductive.
In some specific examples, when the conductive silicon layer is a doped polysilicon material, the amorphization process creates an amorphous material, such as SiOx as a resistive switching layer. In other specific examples, when the conductive silicon layer is a doped silicon-germanium material, the amorphization process creates a SixGeyOz (x, y, z integers) material as a resistive switching material. In some examples, the resulting resistive switching material may have a thickness in the range of approximately 2 nm to approximately 5 nm. In other embodiments, other thicknesses are contemplated, in light of the specific engineering requirements.
Subsequently, an active metal layer (e.g. silver, platinum, palladium, copper, nickel, or the like) is disposed above the upper region (now amorphous layer). One or more second metal layers (e.g. aluminum) may be formed in electrical contact with the active metal layer. A resistive memory device is formed from a lower region of the conductive silicon layer, the non-conductive amorphous layer, and the active metal layer.
In various embodiments, a processor, or the like, may include resistive memories as described herein. Because the resistive memories are relatively non-volatile, the resistive 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 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.
According to one aspect of the invention, a semiconductor fabrication method for forming a resistive memory device is disclosed. One technique includes providing a substrate comprising a first metal material, and forming a conductive silicon-bearing layer on top of the first metal material, wherein the conductive silicon-bearing layer comprises an upper region and a lower region, and wherein the lower region is adjacent to the first metal material. A process includes forming an amorphous layer from the upper region of the conductive silicon-bearing layer, and disposing an active metal material above the amorphous layer.
According to another aspect of the invention, a resistive memory device is described. One device includes a substrate comprising a first metal material, and a monolithic semiconductor layer formed on the first metal material, wherein the monolithic semiconductor layer comprises an upper region and a lower region, wherein the lower region of the monolithic semiconductor layer comprises a conductive silicon-bearing material, and wherein the upper region of the monolithic semiconductor layer comprises a conductive silicon-bearing material subjected to an Argon plasma etch, and wherein the lower region is adjacent to the first metal material. In a device an active metal material disposed above the upper region.
According to yet another aspect of the invention, a resistive memory device formed according to the processes disclosed herein.



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:
FIG. 1 illustrates a cross-section of a process step for forming a switching device according to various embodiments of the present invention;
FIG. 2 illustrates a cross-section of process step for forming a switching device according to various embodiments of the present invention;
FIG. 3 illustrates a cross-section of a process step for forming a switching device according to various embodiments of the present invention;
FIG. 4 illustrates a cross-section of a process step for forming a switching device according to various embodiments of the present invention;
FIG. 5 illustrates a cross-section of a process step for forming a switching device according to various embodiments of the present invention; and
FIG. 6 illustrates a cross-section of an embodiment of the present invention.



DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention is generally related to a memory (switching) device and an apparatus including a memory device. More particularly, embodiments of the present invention provide structures and a methods for forming one or more resistive switching/memory devices each having improved memory retention characteristics. The embodiments described herein are described with respect to fabrication of high density non-volatile memory devices. However, one of ordinary skill in the art will recognize that these devices may be applied to a broad range of applications, such as processing devices, computing devices, or the like.
FIG. 1 illustrates a substrate 100 having a surface region 110. In various embodiments, the substrate 100 can be a semiconductor substrate, such as: a single crystal silicon wafer, a silicon germanium wafer, a silicon-on-insulator substrate, commonly known as SOI, and the like.
Depending on the specific embodiment, the processes described herein are back-end CMOS processes, i.e. processes limited to certain temperature ranges, and the like, that can be performed upon substrates having existing CMOS devices. Accordingly, the substrate 100 may include one or more transistor devices, conductors, or the like, formed below (e.g. 120) surface region 110, or next to surface region 110 (e.g. 130). In some embodiments, the CMOS devices 120 or 130 may include device drivers controlling circuitry for the resistive switching device; processing or computational logic; physical sensors; memories, or the like. In various embodiments, the one or more resistive switching/memory devices formed herein may be operationally coupled to the CMOS devices 120 or 130.
FIG. 2 illustrates a resulting cross-section 200 after a first dielectric material 210 is disposed overlying the surface region 110 of the semiconductor substrate 100. The first dielectric material 210 can be a suitable dielectric material such as silicon oxide, silicon nitride or combinations thereof depending on the embodiment. In various embodiments, the first dielectric material 210 can be deposited using conventional processing techniques such as plasma enhanced chemical vapor deposition; low pressure chemical vapor deposition; or the like depending on engineering requirements. In some examples, silicon oxide may be formed using silane, disilane, a suitable chlorosilane or TEOS, or other suitable silicon bearing materials, depending on the embodiment.
FIG. 3 illustrates a cross-section 300 after a first wiring material 310 is disposed overlying the first dielectric material 210. In various embodiments, the first wiring material 310 may be tungsten, copper, aluminum or other suitable metal materials including alloys thereof. In various embodiments, the first wiring material 310 can be deposited using conventional processing techniques including: physical vapor deposition, evaporation, chemical vapor deposition, or the like; electrochemical methods such as electroplating or electrode-less deposition from a liquid medium, or the like; or other suitable deposition techniques including combinations of the above. In some embodiments, first wiring material 310 may be patterned. Additionally, one or more bather materials/contact materials may be disposed on first wiring material 310 before or after patterning.
In some embodiments of the present invention, a conductive silicon-bearing material 320 may be disposed over the first wiring material 310. In some embodiments of the present invention, conductive material 320 may be a polysilicon, a p-type doped polysilicon, a silicon/germanium alloy or the like. Various methods may be used to dope the polysilicon, including in-situ dopants, ion implantation, and the like. The p-type dopant may be any conventional dopant in various embodiments, such as Boron, or the like. In some embodiments, the thickness of the silicon-bearing material 320 may be within the range of about 3 nm to about 10 nm, or the like. An upper region 340 and a lower region 350 are illustrated.
In some embodiments of the present invention, before conductive silicon layer 320 is formed, a thick dielectric layer, e.g. an oxide layer, may be formed above first wiring material 310. Then a series of vias are etched into the thick oxide layer to expose first wiring material 310. In such cases, the conductive silicon material 320 is formed within the via structures.
In various embodiments, after or when the conductive silicon-bearing material, e.g. doped polysilicon layer is being formed, a thin layer 330 of material may be formed on the top surface of conductive material 320. This growth may be a natural process that occurs between processing steps, or this growth may be intentional performed. In some embodiments, the thickness of the may be controlled. In other words, an etch process (e.g. HF dip, or the like) may be performed to either completely remove the layer before subsequent processes are performed, or the thickness of the layer may brought within a certain thickness range. In some embodiments, the thickness of the layer may be on the order of 0 to 50 angstroms. In some embodiments, the within the device, the thin layer 330 is an oxide, nitride, or the like.
FIG. 4 illustrates a cross-section 400 according to embodiments of the present invention. In FIG. 4, the top surface of the device illustrated in FIG. 3 is subject to an Argon gas plasma etch 410 with a bias power within a range of approximately 30 watts to approximately 120 watts. In other embodiments, the plasma etch may use oxygen, silicon, another noble gas, or the like.
In some embodiments of the present invention, an ion implantation process is performed instead of/or in addition to the plasma etch. The implantation may use Argon-ions or the like. In some embodiments, implantation energy may be within the range 10 to 200 keV.
As illustrated in FIG. 4, upper region 340 of conductive material 320 is affected by the plasma etch/ion implant. In various embodiments, it is believed that the result of the etch/implant is an amorphizing of the conductive silicon material within upper region 410. In other words, a portion of the conductive silicon material within upper region 340 is etched away, and a portion becomes non-conductive, i.e. amorphous silicon layer 430. Although amorphous silicon 430 may still include p-type dopants, the amorphous silicon is non-crystalline, and is non-conductive.
In some specific examples, when conductive material 320 is a doped polysilicon material, the amorphization process creates an amorphous SiOx material. In other specific examples, when conductive material 320 is a doped silicon-germanium material, the amorphization process creates SiOx and/or a SixGeyOz (x, y, z integers) material as the amorphous layer. In some examples, the upper region 410 may have a thickness in the range of approximately 2 nm to approximately 5 nm. In other embodiments, other thicknesses are contemplated, in light of the specific engineering requirements. As will be described below, the amorphous silicon 430 in upper region 340 serves as a resistive switching layer.
In some embodiments, where a via structure is used, conductive material 320 may be planarized with respect to a thick dielectric layer, e.g. an oxide layer, prior to the amorphizing process described above. After amorphizing, the amorphous silicon 430 is exposed for the following steps.
In some embodiments, a pillar-type structure is used. In such embodiments, the amorphous silicon 430 and the lower region 350 may be etched to form a series of pillar-type structures overlying first wiring layer 310. In such embodiments, a thick dielectric layer is formed over and between the pillar-type structures, and one or more CMP processes may be performed to expose a top surface of amorphous silicon 430 for the following steps.
In some embodiments, amorphous silicon 430 (the amorphous layer) has a thickness within the range of approximately 2 to approximately 10 nanometers, approximately 30 Angstroms to approximately 40 Angstroms, or the like depending upon specific device engineering requirements or design. In some embodiments, a thickness of lower region 350 is typically greater than a thickness of upper region 340.
In some experimental studies, where an oxide layer 330 is present, oxide layer 330 above upper region 340 disappears, and an atomic composition of amorphous silicon 430 reveals primarily silicon and oxygen. In various embodiments, amorphous silicon 430 is the switching material for this device.
FIG. 5 illustrates a cross-section 500 according to various embodiments of the present invention. More specifically, as illustrated in FIG. 5, a conductive material 510 is disposed above amorphous silicon 430. In a specific embodiment, for amorphous silicon switching material, conductive material 510 can comprise a silver material, and in other embodiments, materials including silver, platinum, palladium, copper or nickel, or a combination may be used for conductive material.
Conductive material 510 can be deposited using a physical deposition process such as sputtering or evaporation. Conductive material 510 (e.g. silver) may also be formed using a chemical deposition process such as chemical vapor deposition, electrochemical such as electroplating, electrodeless deposition, or a combination depending on the application.
In some embodiments, a thin layer of material may be present prior to the deposition of conductive material 510. This thin layer may be within the range of approximately 5 nm to approximately 25 Angstroms, approximately 40 A to 30 A, approximately 30 A, or the like. In some embodiments, the thin layer serves to reduce the diffusion or agglomeration of conductive material 510 (e.g. silver) into switching material 430 during fabrication of the disclosed structures. In such embodiments, as back end fabrication steps may include high temperature operations, the thin layer reduces the migration of the metallic ions into the switching material 430. In some embodiments, the thin layer also serves to restrict or control where metallic ions migrate into switching material 430 during operation of the device. As disclosed in co-pending U.S. patent application Ser. No. 12/894,098, filed Sep. 29, 2010, assigned to the same assignee, and incorporated by reference herein, for all purposes, during operation of the device, a thin oxide layer is used to control a conductive path from a metallic layer to the switching layer.
In various embodiments of the present invention, the thin layer may be a layer of oxide, carbon, nitride or other relative stable material. These materials may be formed via a plasma enhanced chemical vapor deposition process, an atomic layer deposition process, a spin coating process, a plasma oxidation process, a physical vapor deposition process, a naturally occurring growth, or the like. In some embodiments, the formed oxide may be subsequently etched until the desired thickness is obtained for the thin layer. In some examples, an Argon etch may be used. In some embodiments, the conductive material 510 is thus formed or deposited on top of the thin layer that is specifically grown, formed, deposited, or naturally occurring upon switching material 430.
In various embodiments, one or more barrier/contact materials may be formed overlying the conductive material 510. In some examples, barrier/contact materials protect conductive material 510 from oxidation, serve as a polish stop material in a subsequent step for a CMP process, or the like. In some embodiments, barrier/contact material can be titanium, titanium nitride, tantalum or tantalum nitride, tungsten, or tungsten nitride, or any suitable barrier material and can be formed using a chemical deposition such as atomic layer deposition, chemical vapor deposition, and others, or a physical deposition such as sputtering, depending on the application.
In a specific embodiment, an embodiment may include subjecting a stack of material comprising one or more barrier/contact materials, amorphous material 430, lower region 420, conductive material 510, and/or one or more barrier/contact materials to a patterning and etch process to form a plurality of pillar structures above first wiring material 310. The shape of the cross section shape of pillar structures may be approximately square, rectangular, circular, hexagonal, or other similar shape. Within the pillar structures, lower region 420, amorphous material 430, and conductive material 510 form the switching device. In various embodiments, the pillar structures can have a feature size of less than about 250 nm and preferably about 90 nm, or even 40 nm, depending on the technology node adopted. The first wiring layer 310 structure can have a width of about 90 nm or greater. Subsequently, in some embodiments, a thick dielectric is deposited to laterally isolate the pillar structures, and one or more planarization processes are performed to expose a top surface of conductive material 510.
FIG. 6 illustrates a cross-section 600 of an embodiment of the present invention. In FIG. 6, in some embodiments, a second wiring material 520 is disposed in electrical contact with conductive material 510 (sometimes with intermediary barrier/contact materials). As can be seen, the pillars of FIG. 5 are electrically isolated (e.g. by an oxide, or the like). In various embodiments, the second wiring material 520 may be tungsten, copper, aluminum or other suitable metal materials including alloys thereof. In various embodiments, the second wiring material 520 can be deposited using conventional processing techniques including: physical vapor deposition, evaporation, chemical vapor deposition, or the like; electrochemical methods such as electroplating or electrode-less deposition from a liquid medium, or the like; or other suitable deposition techniques including combinations of the above. In some embodiments, second wiring material 520 may be patterned. Additionally, one or more barrier materials/contact materials may be disposed on second wiring material 520 before or after patterning, such as tungsten.
In some embodiments, first wiring material 310 is patterned and extends in a first direction and second wiring material 520 is patterned and extends in a second direction. The first direction and the second direction are characterized by an angle between them. In some embodiments the angle may be 90 degrees, 30 degrees, or the like.
In a specific embodiment, the top wiring structure, the bottom wiring structure and the switching element sandwiched between the first wiring structure and the second wiring structure provide for a switching device for a non-volatile memory device. Of course one skilled in the art would recognize other variations, modifications, and alternatives. 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 method for forming a resistive memory device comprising:
providing a substrate comprising a first metal material;
forming a conductive silicon-bearing layer on top of the first metal material, wherein the conductive silicon-bearing layer comprises an upper region and a lower region, and wherein the lower region is adjacent to the first metal material;
forming an amorphous layer from the upper region of the conductive silicon-bearing layer; and
disposing an active metal material above the amorphous layer.

2. The method of claim 1
wherein a barrier layer is formed on the amorphous layer prior to the disposing the active metal material above the amorphous layer; and
wherein the barrier layer comprises a nitride layer.

3. The method of claim 1 wherein the barrier layer has a thickness within the range of approximately 20 Angstroms to approximately 50 Angstroms.

4. The method of claim 1
wherein the active metal material comprises a metal selected from a group consisting of: aluminum, silver, platinum, palladium, copper, and nickel.

5. The method of claim 1 wherein forming the amorphous layer from the upper region comprises: performing an Argon, silicon, and/or oxygen plasma etch on an exposed surface of the conductive silicon-bearing layer.

6. The method of claim 1
wherein forming the amorphous layer from the upper region comprises: performing an Argon plasma etch on an exposed surface of the conductive silicon-bearing layer; and
wherein the plasma etch comprises a bias power within a range of approximately 30 watts to approximately 120 watts.

7. The method of claim 1
wherein forming the amorphous layer from the upper region comprises: performing an ion implantation on the upper region of the conductive silicon-bearing; and
wherein an ion for the ion implant is selected from a group consisting: Argon, silicon, and oxygen.

8. The method of claim 1 wherein the amorphous layer has a thickness within the range of approximately 2 to approximately 10 nanometers.

9. The method of claim 1 wherein the amorphous layer has a thickness within the range of approximately 30 Angstroms to approximately 40 Angstroms.

10. The method of claim 1
wherein the conductive silicon-bearing layer comprises SixGex-1;
wherein the conductive silicon-bearing layer comprises a p-type dopant; and
wherein the amorphous layer comprises a silicon oxide.

11. A method for fabricating a device comprising:
providing a substrate including a plurality of CMOS devices;
forming a resistive memory upon the substrate comprising:
forming a first metal material;
forming a monolithic conductive silicon-bearing layer on top of the first metal material;
forming an amorphous silicon and oxygen-bearing layer in a portion of the monolithic conductive silicon-bearing layer; and
disposing an active metal material above the amorphous silicon and oxygen-bearing layer; and
coupling the resistive memory to at least one of the plurality of CMOS devices.

12. The method of claim 11 further comprising after the forming the amorphous silicon and oxygen-bearing layer, forming a barrier layer on the portion of the monolithic conductive silicon-bearing layer, prior to the disposing the active metal material.

13. The method of claim 11 wherein the barrier layer is selected from a group of materials consisting of: a nitride, an oxide, titanium, titanium nitride, tantalum, tantalum nitride, tungsten, or tungsten nitride.

14. The method of claim 11
wherein the active metal material comprises a metal selected from a group consisting of: aluminum, silver, platinum, palladium, copper, and nickel.

15. The method of claim 11 wherein the forming the amorphous layer from the upper region comprises an etch on an exposed surface of the monolithic conductive silicon-bearing layer, wherein the etch includes a material selected from a group consisting of: argon, silicon, oxygen.

16. The method of claim 11
wherein the forming the amorphous silicon and oxygen-bearing layer comprises: performing an Argon plasma etch on an exposed surface of the monolithic conductive silicon-bearing layer using a bias power within a range of approximately 30 watts to approximately 120 watts.

17. The method of claim 11
wherein the forming the amorphous silicon and oxygen-bearing layer comprises: performing an ion implantation on an exposed surface of the monolithic conductive silicon-bearing layer; and
wherein an ion for the ion implantation is selected from a group consisting: argon, silicon, and oxygen.

18. The method of claim 11 wherein the amorphous silicon and oxygen-bearing layer has a thickness within the range of approximately 2 to approximately 10 nanometers.

19. The method of claim 11 wherein the amorphous silicon and oxygen-bearing layer has a thickness within the range of approximately 30 Angstroms to approximately 40 Angstroms.

20. The method of claim 11
wherein the monolithic conductive silicon-bearing layer comprises a p-doped SixGex-1; and
wherein the amorphous silicon and oxygen-bearing layer comprises SixGeyOz (x, y, z integers.

21. A method for forming a resistive memory device comprising:
providing a substrate comprising a first metal material;
forming a conductive silicon-bearing layer on top of the first metal material, wherein the conductive silicon-bearing layer comprises an upper region and a lower region, and wherein the lower region is adjacent to the first metal material;
forming an amorphous layer from the upper region of the conductive silicon-bearing layer, wherein forming the amorphous layer from the upper region comprises a process selected from a group consisting of:
performing an Argon, silicon, and/or oxygen plasma etch on an exposed surface of the conductive silicon-bearing layer; and
performing an ion implantation on the upper region of the conductive silicon-bearing, and wherein an ion for the ion implant is selected from a group consisting: Argon, silicon, and oxygen; and
disposing an active metal material above the amorphous layer.

22. The method of claim 21
wherein a barrier layer is formed on the amorphous layer prior to the disposing the active metal material above the amorphous layer; and
wherein the barrier layer comprises a nitride layer.

23. The method of claim 21 wherein the barrier layer has a thickness within the range of approximately 20 Angstroms to approximately 50 Angstroms.

24. The method of claim 21
wherein the active metal material comprises a metal selected from a group consisting of: aluminum, silver, platinum, palladium, copper, and nickel.

25. The method of claim 21 wherein the amorphous layer has a thickness within the range of approximately 2 to approximately 10 nanometers.

26. The method of claim 21 wherein the amorphous layer has a thickness within the range of approximately 30 Angstroms to approximately 40 Angstroms.

27. The method of claim 21
wherein the conductive silicon-bearing layer comprises polycrystalline silicon and germanium.

28. The method of claim 21 wherein the amorphous layer comprises SiOx.

29. The method of claim 21 further comprising forming a barrier layer on top of the active metal layer, wherein a material for the barrier layer is selected from a group consisting of: titanium, titanium nitride, tantalum, tantalum nitride, tungsten, and tungsten nitride.

30. The method of claim 21 wherein a thickness of the upper region of the conductive silicon-bearing layer is less than a thickness of the lower region of the conductive silicon-bearing layer.