Patent Application
20100032640
This invention relates to non-volatile memories, and more particularly to a memory cell that includes a carbon-based memory element, and methods of forming the same.
Non-volatile memories formed from reversible resistance switching elements are known. For example, U.S. patent application Ser. No. 11/968,154, filed Dec. 31, 2007, titled “Memory Cell That Employs A Selectively Fabricated Carbon Nano-Tube Reversible Resistance Switching Element And Methods Of Forming The Same” (the “'154 Application”), which is hereby incorporated by reference herein in its entirety for all purposes, describes a rewriteable non-volatile memory cell that includes a diode coupled in series with a carbon-based reversible resistivity switching material.
However, fabricating memory devices from carbon-based materials is technically challenging, and improved methods of forming memory devices that employ carbon-based materials are desirable.
In a first aspect of the invention, a method of forming a memory cell is provided, the method including forming a layer of carbon material above a substrate, forming a barrier layer above the carbon layer, forming a hardmask layer above the barrier layer, forming a photoresist layer above the hardmask layer, patterning and developing the photoresist layer to form a photoresist region, patterning and etching the hardmask layer to form a hardmask region, and using an ashing process to remove the photoresist region while the barrier layer remains above the carbon layer.
In a second aspect of the invention, a method of forming a memory cell is provided, the method including forming a layer of carbon material above a substrate, forming a photoresist layer above the carbon layer, patterning and developing the photoresist layer to form a photoresist region, patterning and etching the carbon layer using the photoresist region, and performing an ashing process to remove the photoresist region without substantially damaging an exposed sidewall of the etched carbon layer.
Other features and aspects of the present invention will become more fully apparent from the following detailed description, the appended claims and the accompanying drawings.
Features of the present invention can be more clearly understood from the following detailed description considered in conjunction with the following drawings, in which the same reference numerals denote the same elements throughout, and in which:
Carbon films such as amorphous carbon (“aC”) containing nanocrystalline graphene (referred to herein as “graphitic carbon”), graphene, graphite, carbon nano-tubes, amorphous diamond-like carbon (“DLC”) (described below), silicon carbide, boron carbide and other similar carbon-based materials may exhibit resistivity-switching behavior that may make such materials suitable for use in microelectronic non-volatile memories.
Indeed, some carbon-based materials have demonstrated reversible resistivity-switching memory properties on lab-scale devices with a 100× separation between ON and OFF states and mid-to-high range resistance changes. Such a separation between ON and OFF states renders carbon-based materials viable candidates for memory cells formed using the carbon materials in memory elements in series with steering elements, such as tunnel junctions, diodes, thin film transistors, or the like.
A carbon-based resistivity-switching material may be characterized by its ratio of forms of carbon-carbon bonding. Carbon typically bonds to carbon to form either an sp2-bond (a trigonal carbon-carbon double bond (“C═C”)) or an sp3-bond (a tetrahedral carbon-carbon single bond (“C—C”)). In each case, a ratio of sp2-bonds to sp3-bonds can be determined via Raman spectroscopy by evaluating the D and G bands. In some embodiments, the range of materials may include those having a ratio such as MyNz where M is the sp3 material and N is the sp2 material and y and z are any fractional value from zero to 1 as long as y+z=1. To provide sufficient resistivity-switching behavior useful in a memory device, the carbon-based material should have a relatively high concentration of sp2 graphene crystallinity. DLC tends to be sp3-hybridized, and to be amorphous with respect to long range order, and also has found to be switchable.
A carbon-based memory element may be formed by arranging a carbon-based material between two electrodes to form a metal-insulator-metal (“MIM”) structure. In such a configuration, the carbon-based material sandwiched between the two metal or otherwise conducting layers serves as a reversible resistance-switching element. A memory cell may then be formed by coupling the MIM structure in series with a steering element, such as a diode.
Semiconductor fabrication techniques may be used to fabricate carbon-based memory cells. For example, semiconductor processing techniques may be used to fabricate a pillar that includes a vertically oriented diode and a carbon-based resistivity-switching layer coupled in series between a bottom conductor and a top conductor. In particular, such pillars could be formed by depositing the various layers that constitute the memory cell on a substrate, including a carbon material layer, depositing photoresist on top of the layers, patterning the photoresist, etching to form the pillars, and then removing the photoresist.
In practice, however, fabricating such carbon-based memory cells is technically challenging. In particular, after the pillars have been formed, the photoresist must be removed. In conventional semiconductor processing techniques, photoresist typically is removed by using a plasma ashing process. Conventional plasma ashing processes, however, may damage the exposed carbon material layer in the pillars. Indeed, carbon-based materials historically have been used in the semiconductor industry as hard masks that are typically removed by ashing. Thus, if conventional plasma ashing processes are used to remove the photoresist, the ashing process may cause severe undercutting of the sidewalls of the exposed carbon material layer, and may render the memory cell inoperative.
Therefore, improved techniques for forming carbon-based memory cells are desired that may be used with conventional semiconductor processing techniques.
Exemplary methods in accordance with this invention protect carbon-based materials from damage during subsequent processing steps. In a first exemplary method of this invention, a barrier layer is formed above a carbon-based material layer, a hard mask layer is formed above the barrier layer, and photoresist is deposited above the hard mask layer. The photoresist is patterned and developed to form patterned photoresist regions. The patterned photoresist regions are then used to pattern and etch the hardmask layer to form patterned hardmask regions. The barrier layer is not etched, and thus the carbon-based material layer remains covered by the barrier material. The patterned photoresist regions are then removed, such as by a conventional ashing process. The patterned hardmask regions are then used to pattern and etch the carbon-based material layer. In this regard, the carbon-based material layer remains protected during the ashing process.
In an alternative method of this invention, photoresist is deposited a carbon-based material layer, and the photoresist is patterned and developed to form patterned photoresist. The patterned photoresist regions are then used to pattern and etch the carbon-based material layer. The patterned photoresist regions are then removed by a two-step ash process that removes the photoresist without substantially damaging the carbon-based material layer.
For example, carbon-based reversible resistivity-switching material of element 12 may be in an initial, low-resistivity state upon fabrication. Upon application of a first voltage and/or current, the material is switchable to a high-resistivity state. Application of a second voltage and/or current may return reversible resistivity switching material to a low-resistivity state. Alternatively, carbon-based reversible resistance-switching element 12 may be in an initial, high-resistance state upon fabrication that is reversibly switchable to a low-resistance state upon application of the appropriate voltage(s) and/or current(s). When used in a memory cell, one resistance state may represent a binary “0,” whereas another resistance state may represent a binary “1,” although more than two data/resistance states may be used. Numerous reversible resistivity switching materials and operation of memory cells employing reversible resistance switching elements are described, for example, in U.S. patent application Ser. No. 11/125,939, filed May 9, 2005 and titled “Rewriteable Memory Cell Comprising A Diode And A Resistance Switching Material” (the “'939 Application”), which is hereby incorporated by reference herein in its entirety for all purposes.
Steering element 14 may include a thin film transistor, a diode, metal-insulator-metal tunneling current device, or another similar steering element that exhibits non-ohmic conduction by selectively limiting the voltage across and/or the current flow through carbon-based reversible resistance-switching element 12. In this manner, memory cell 10 may be used as part of a two or three dimensional memory array and data may be written to and/or read from memory cell 10 without affecting the state of other memory cells in the array.
Exemplary embodiments of memory cell 10, carbon-based reversible resistance-switching element 12 and steering element 14 are described below with reference to
Carbon-based reversible resistance-switching element 12 may include a carbon-based material suitable for use in a memory cell. In exemplary embodiments of this invention, carbon-based reversible resistance-switching element 12 may include graphitic carbon. For example, in some embodiments, graphitic carbon reversible resistivity switching materials may be formed as described in U.S. patent application Ser. No. 12/499,467, filed Jul. 8, 2009 and titled “Carbon-Based Resistivity-Switching Materials And Methods Of Forming The Same” (the “'467 application”) (Docket No. SD-MXA-294), which is hereby incorporated by reference herein in its entirety for all purposes. In other embodiments, carbon-based reversible resistance-switching element 12 may include other carbon-based materials such as graphene, graphite, carbon nano-tube materials, DLC, silicon carbide, boron carbide, or other similar carbon-based materials. For simplicity, carbon-based reversible resistance-switching element 12 will be referred to in the remaining discussion interchangeably as “carbon element 12,” or “carbon layer 12.”
In an exemplary embodiment of this invention, steering element 14 includes a diode. In this discussion, steering element 14 is sometimes referred to as “diode 14.” Diode 14 may include any suitable diode such as a vertical polycrystalline p-n or p-i-n diode, whether upward pointing with an n-region above a p-region of the diode or downward pointing with a p-region above an n-region of the diode. For example, diode 14 may include a heavily doped n+ polysilicon region 14a, a lightly doped or an intrinsic (unintentionally doped) polysilicon region 14b above the n+ polysilicon region 14a, and a heavily doped p+ polysilicon region 14c above intrinsic region 14b. It will be understood that the locations of the n+ and p+ regions may be reversed.
First conductor 20 and/or second conductor 22 may include any suitable conductive material such as tungsten, any appropriate metal, heavily doped semiconductor material, a conductive silicide, a conductive silicide-germanide, a conductive germanide, or the like. In the embodiment of
For example,
For example, in some embodiments, the memory levels may be formed as described in U.S. Pat. No. 6,952,030, titled “High-Density Three-Dimensional Memory Cell,” which is hereby incorporated by reference herein in its entirety for all purposes. For instance, the upper conductors of a first memory level may be used as the lower conductors of a second memory level that is positioned above the first memory level as shown in
A monolithic three dimensional memory array is one in which multiple memory levels are formed above a single substrate, such as a wafer, with no intervening substrates. The layers forming one memory level are deposited or grown directly over the layers of an existing level or levels. In contrast, stacked memories have been constructed by forming memory levels on separate substrates and adhering the memory levels atop each other, as in Leedy, U.S. Pat. No. 5,915,167, titled “Three Dimensional Structure Memory.” The substrates may be thinned or removed from the memory levels before bonding, but as the memory levels are initially formed over separate substrates, such memories are not true monolithic three dimensional memory arrays.
First conductor 20 may include any suitable conductive material such as tungsten, any appropriate metal, heavily doped semiconductor material, a conductive silicide, a conductive silicide-germanide, a conductive germanide, or the like. Second conductor 22 includes a barrier layer 26, which may include titanium nitride or other similar barrier layer material, and conductive layer 140, which may include any suitable conductive material such as tungsten, any appropriate metal, heavily doped semiconductor material, a conductive silicide, a conductive silicide-germanide, a conductive germanide, or the like.
Diode 14 may be a vertical p-n or p-i-n diode, which may either point upward or downward. In the embodiment of
In some embodiments, diode 14 may be formed from a polycrystalline semiconductor material such as polysilicon, a polycrystalline silicon-germanium alloy, polygermanium or any other suitable material. For example, diode 14 may include a heavily doped n+ polysilicon region 14a, a lightly doped or an intrinsic (unintentionally doped) polysilicon region 14b above the n+ polysilicon region 14a, and a heavily doped p+ polysilicon region 14c above intrinsic region 14b. It will be understood that the locations of the n+ and p+ regions may be reversed.
In some embodiments, a thin germanium and/or silicon-germanium alloy layer (not shown) may be formed on n+ polysilicon region 14a to prevent and/or reduce dopant migration from n+ polysilicon region 14a into intrinsic region 14b. Use of such a layer is described, for example, in U.S. patent application Ser. No. 11/298,331, filed Dec. 9, 2005 and titled “Deposited Semiconductor Structure To Minimize N-Type Dopant Diffusion And Method Of Making” (the “'331 Application”), which is hereby incorporated by reference herein in its entirety for all purposes. In some embodiments, a few hundred angstroms or less of silicon-germanium alloy with about 10 at % or more of germanium may be employed.
A barrier layer 28, such as titanium nitride, tantalum nitride, tungsten nitride, or other similar barrier layer material, may be formed between the first conductor 20 and the n+ region 14a (e.g., to prevent and/or reduce migration of metal atoms into the polysilicon regions).
If diode 14 is fabricated from deposited silicon (e.g., amorphous or polycrystalline), a silicide layer 50 may be formed on diode 14 to place the deposited silicon in a low resistivity state, as fabricated. Such a low resistivity state allows for easier programming of memory cell 10, as a large voltage is not required to switch the deposited silicon to a low resistivity state. For example, a silicide-forming metal layer 52 such as titanium or cobalt may be deposited on p+ polysilicon region 14c. In some embodiments, an additional nitride layer (not shown) may be formed at a top surface of silicide-forming metal layer 52. In particular, for highly reactive metals, such as titanium, an additional cap layer such as TiN layer may be formed on silicide-forming metal layer 52. Thus, in such embodiments, a Ti/TiN stack is formed on top of p+ polysilicon region 14c.
A rapid thermal anneal (“RTA”) step may then be performed to form silicide regions by reaction of silicide-forming metal layer 52 with p+ region 14c. The RTA step may be performed at a temperature between about 650° C. to about 750° C., more generally between about 600° C. to about 800° C., preferably at about 750° C., for a duration between about 10 seconds to about 60 seconds, more generally between about 10 seconds to about 90 seconds, preferably about 1 minute, and causes silicide-forming metal layer 52 and the deposited silicon of diode 14 to interact to form silicide layer 50, consuming all or a portion of the silicide-forming metal layer 52.
As described in U.S. Pat. No. 7,176,064, titled “Memory Cell Comprising A Semiconductor Junction Diode Crystallized Adjacent To A Silicide,” which is hereby incorporated by reference herein in its entirety for all purposes, silicide-forming materials such as titanium and/or cobalt react with deposited silicon during annealing to form a silicide layer. The lattice spacing of titanium silicide and cobalt silicide are close to that of silicon, and it appears that such silicide layers may serve as “crystallization templates” or “seeds” for adjacent deposited silicon as the deposited silicon crystallizes (e.g., silicide layer 50 enhances the crystalline structure of silicon diode 14 during annealing). Lower resistivity silicon thereby is provided. Similar results may be achieved for silicon-germanium alloy and/or germanium diodes.
In embodiments in which a nitride layer was formed at a top surface of silicide-forming metal layer 52, following the RTA step, the nitride layer may be stripped using a wet chemistry. For example, if silicide-forming metal layer 52 includes a TiN top layer, a wet chemistry (e.g., ammonium, peroxide, water in a 1:1:1 ratio) may be used to strip any residual TiN.
A barrier layer 33, such as titanium nitride, tantalum nitride, tungsten nitride, or other similar barrier layer material, may be formed above carbon layer 12.
In exemplary methods in accordance with this invention, described in more detail with respect to
In an alternative method of this invention, photoresist is deposited on metal layer 35, and the photoresist is patterned and developed to form patterned photoresist. The patterned photoresist regions are then used to pattern and etch metal layer 35, barrier layer 33, carbon layer 12, barrier layer 24, silicide forming metal layer 52, silicide layer 50, diode 14 and barrier layer 28. The patterned photoresist regions are then removed by a two-step “engineered ash” process that removes the photoresist without substantially damaging carbon layer 12.
Referring now to
With reference to
Isolation layer 102 is formed above substrate 100. In some embodiments, isolation layer 102 may be a layer of silicon dioxide, silicon nitride, silicon oxynitride or any other suitable insulating layer.
Following formation of isolation layer 102, an adhesion layer 104 is formed over isolation layer 102 (e.g., by physical vapor deposition (“PVD”) or another method). For example, adhesion layer 104 may be about 20 to about 500 angstroms, and preferably about 100 angstroms, of titanium nitride or another suitable adhesion layer such as tantalum nitride, tungsten nitride, combinations of one or more adhesion layers, or the like. Other adhesion layer materials and/or thicknesses may be employed. In some embodiments, adhesion layer 104 may be optional.
After formation of adhesion layer 104, a conductive layer 106 is deposited over adhesion layer 104. Conductive layer 106 may include any suitable conductive material such as tungsten or another appropriate metal, heavily doped semiconductor material, a conductive silicide, a conductive silicide-germanide, a conductive germanide, or the like deposited by any suitable method (e.g., chemical vapor deposition (“CVD”), PVD, etc.). In at least one embodiment, conductive layer 106 may comprise about 200 to about 2500 angstroms of tungsten. Other conductive layer materials and/or thicknesses may be used.
Following formation of conductive layer 106, adhesion layer 104 and conductive layer 106 are patterned and etched. For example, adhesion layer 104 and conductive layer 106 may be patterned and etched using conventional lithography techniques, with a soft or hard mask, and wet or dry etch processing. In at least one embodiment, adhesion layer 104 and conductive layer 106 are patterned and etched to form substantially parallel, substantially co-planar first conductors 20. Exemplary widths for first conductors 20 and/or spacings between first conductors 20 range from about 200 to about 2500 angstroms, although other conductor widths and/or spacings may be used.
After first conductors 20 have been formed, a dielectric layer 58a is formed over substrate 100 to fill the voids between first conductors 20. For example, approximately 3000-7000 angstroms of silicon dioxide may be deposited on the substrate 100 and planarized using chemical mechanical polishing or an etchback process to form a planar surface 110. Planar surface 110 includes exposed top surfaces of first conductors 20 separated by dielectric material (as shown). Other dielectric materials such as silicon nitride, silicon oxynitride, low K dielectrics, etc., and/or other dielectric layer thicknesses may be used. Exemplary low K dielectrics include carbon doped oxides, silicon carbon layers, or the like.
In other embodiments of the invention, first conductors 20 may be formed using a damascene process in which dielectric layer 58a is formed, patterned and etched to create openings or voids for first conductors 20. The openings or voids then may be filled with adhesion layer 104 and conductive layer 106 (and/or a conductive seed, conductive fill and/or barrier layer if needed). Adhesion layer 104 and conductive layer 106 then may be planarized to form planar surface 110. In such an embodiment, adhesion layer 104 will line the bottom and sidewalls of each opening or void.
Following planarization, the diode structures of each memory cell are formed. With reference to
After deposition of barrier layer 28, deposition of the semiconductor material used to form the diode of each memory cell begins (e.g., diode 14 in
With reference to
After deposition of n+ silicon layer 14a, a lightly doped, intrinsic and/or unintentionally doped silicon layer 14b may be formed over n+ silicon layer 14a. In some embodiments, intrinsic silicon layer 14b may be in an amorphous state as deposited. In other embodiments, intrinsic silicon layer 14b may be in a polycrystalline state as deposited. CVD or another suitable deposition method may be employed to deposit intrinsic silicon layer 14b. In at least one embodiment, intrinsic silicon layer 14b may be about 500 to about 4800 angstroms, preferably about 2500 angstroms, in thickness. Other intrinsic layer thicknesses may be used.
A thin (e.g., a few hundred angstroms or less) germanium and/or silicon-germanium alloy layer (not shown) may be formed on n+ silicon layer 14a prior to depositing intrinsic silicon layer 14b to prevent and/or reduce dopant migration from n+ silicon layer 14a into intrinsic silicon layer 14b (as described in the '331 Application, previously incorporated).
Heavily doped, p-type silicon may be either deposited and doped by ion implantation or may be doped in situ during deposition to form a p+ silicon layer 14c. For example, a blanket p+ implant may be employed to implant boron a predetermined depth within intrinsic silicon layer 14b. Exemplary implantable molecular ions include BF2, BF3, B and the like. In some embodiments, an implant dose of about 1-5×1015 ions/cm2 may be employed. Other implant species and/or doses may be used. Further, in some embodiments, a diffusion process may be employed. In at least one embodiment, the resultant p+ silicon layer 14c has a thickness of about 100-700 angstroms, although other p+ silicon layer sizes may be used.
Following formation of p+ silicon layer 14c, a silicide-forming metal layer 52 is deposited over p+ silicon layer 14c. Exemplary silicide-forming metals include sputter or otherwise deposited titanium or cobalt. In some embodiments, silicide-forming metal layer 52 has a thickness of about 10 to about 200 angstroms, preferably about 20 to about 50 angstroms and more preferably about 20 angstroms. Other silicide-forming metal layer materials and/or thicknesses may be used. A nitride layer (not shown) may be formed at the top of silicide-forming metal layer 52.
Following formation of silicide-forming metal layer 52, an RTA step may be performed to form silicide layer 50, consuming all or a portion of the silicide-forming metal layer 52. The RTA step may be performed at a temperature between about 650° C. and about 750° C., more generally between about 600° C. and about 800° C., preferably at about 750° C., for a duration between about 10 seconds to about 60 seconds, more generally between about 10 seconds to about 90 seconds, preferably about 60 seconds. Following the RTA step, any residual nitride layer from silicide-forming metal layer 52 may be stripped using a wet chemistry, as described above, and as is known in the art.
Following the RTA step and the nitride strip step, a barrier layer 24 is deposited. Barrier layer 24 may be about 20 to about 500 angstroms, and preferably about 200 angstroms, of titanium nitride or another suitable barrier layer such as tantalum nitride, tungsten nitride, combinations of one or more barrier layers, barrier layers in combination with other layers such as titanium/titanium nitride, tantalum/tantalum nitride or tungsten/tungsten nitride stacks, or the like. Other barrier layer materials and/or thicknesses may be employed. Any suitable method may be used to form barrier layer 24. For example, PVD, atomic layer deposition (“ALD”), or the like may be used.
Next, carbon layer 12 is deposited over barrier layer 24. Carbon layer 12 may be formed by a PECVD method, for example. Other methods may be used, including, without limitation, sputter deposition from a target, PVD, CVD, arc discharge techniques, and laser ablation. Other methods may be used to form carbon layer 12, such as a damascene integration method, for example. Carbon layer 12 may include graphitic carbon. In alternative embodiments, other carbon-based materials may be used, such as graphene, graphite, carbon nano-tube materials, DLC or other similar carbon-based materials. Carbon layer 12 is formed having a thickness between about 100 and about 600 angstroms, more generally between about 1 and about 1000 angstroms. Other thicknesses may be used.
Referring again to
Next, a metal layer 35 may be deposited over barrier layer 33. For example, between about 800 to about 1200 angstroms, more generally between about 500 angstroms to about 1500 angstroms, of tungsten may be deposited on barrier layer 33. Other materials and thicknesses may be used. Any suitable method may be used to form metal layer 35. For example, CVD, PVD, or the like may be employed. As described in more detail below, metal layer 35 may be used as a hard mask layer, and also may be used as a stop during a subsequent chemical mechanical planarization (“CMP”) step. A hard mask is an etched layer which serves to pattern the etch of an underlying layer.
In accordance with this invention, processing methods are used to protect carbon layer 12 from damage during subsequent processing steps. In an exemplary method of this invention, a hard mask is used to avoid damage to carbon layer 12 during subsequent processing steps. In an alternative method of this invention, an “engineered ash” process is used that removes photoresist, without causing substantial damage carbon layer 12. Each of these will be discussed in turn.
In a first exemplary method of this invention, and continuing to refer to
After depositing dielectric hard mask layer 94, a photoresist layer 96 is formed on hard mask layer 94. Photoresist layer 96 may be between about 200 to 2000 angstroms of any suitable positive or negative resist material, such as polymethylmethacrylate (“PMMA”), or other photosensitive organic polymers known in the art. Other photoresist layer materials and/or thicknesses may be employed. Photoresist layer 96 may be formed using a spin-on technique or other similar method.
Referring now to
With reference to
After hard mask layer 94 is etched, photoresist regions 96 are removed. Conventional plasma ashing techniques, in which the substrate is exposed to an oxidative or reductive plasma etch, may be used to remove photoresist layer 96. Because carbon layer 12 remains covered (e.g., by metal layer 35 and barrier layer 33) during the ashing step, the ashing process does not damage carbon layer 12.
After photoresist regions 96 have been removed, dielectric hardmask regions 94 remain, as illustrated in
One or more etch steps may be performed. In the exemplary embodiment, metal layer 35, barrier layer 33, carbon layer 12, barrier layer 24, silicide-forming metal layer 52, diode layers 14a-14c, and barrier layer 28 are etched in a single etch step to the top surface of dielectric layer 58a, to form substantially parallel pillars 132 having a width substantially equal to the width of conductors 20 below, as illustrated in
The memory cell layers may be etched using chemistries selected to minimize or avoid damage to carbon material. For example, O2, CO, CO2, N2, or H2, or other similar chemistries may be used. In embodiments in which CNT material is used in the memory cells, oxygen (“O2”), boron trichloride (“BCl3”) and/or chlorine (“Cl2”) chemistries, or other similar chemistries, may be used. Any suitable etch parameters, flow rates, chamber pressures, power levels, process temperatures, and/or etch rates may be used. Exemplary methods for etching carbon material are described, for example, in U.S. patent application Ser. No. 12/415,964, “Electronic Devices Including Carbon-Based Films Having Sidewall Liners, and Methods of Forming Such Devices,” filed Mar. 31, 2009 (Docket No. SD-MXA-315), which is hereby incorporated by reference in its entirety for all purposes.
After the memory cell layers have been etched, pillars 132 may be cleaned. In some embodiments, a dilute hydrofluoric/sulfuric acid clean is performed. Post-etch cleaning may be performed in any suitable cleaning tool, such as a Raider tool, available from Semitool of Kalispell, Mont. Exemplary post-etch cleaning may include using ultra-dilute sulfuric acid (e.g., about 1.5-1.8 wt %) for about 60 seconds and ultra-dilute hydrofluoric (“HF”) acid (e.g., about 0.4-0.6 wt %) for about 60 seconds. Megasonics may or may not be used. Alternatively, H2SO4 may be used.
After pillars 132 have been cleaned, an in-situ anneal or degas in vacuum step may be performed. Carbon material tends to absorb moisture, especially during a wet clean process. This is problematic, because trapped moisture may result in de-lamination of carbon material and degradation in switching. In-situ annealing or degas in vacuum helps to drive out moisture before the next process step. In particular, the in-situ anneal or degas in vacuum is performed in the chamber of the next processing step. Degas in vacuum can also be performed in a transfer chamber or loadlock mounted on the same platform as that process chamber. For example, if the next processing step is formation of a sidewall liner, the in-situ anneal is performed in the chamber used to form the sidewall liner. The in-situ anneal may be performed at a temperature between about 200° C. and about 350° C., more generally between about 200° C. and about 450° C., for a duration between about 1 to about 2 minutes, more generally between about 30 seconds and about 5 minutes, at a pressure of between about 0.1 mT to about 10 T, more generally between about 0.1 mT to about 760 T. Alternatively, the in-situ anneal may be performed in an environment containing Ar, He, or N2, or a forming gas containing H2 and N2, at a flow rate of between about 1000 to about 8000 sccm, more generally between about 1000-20000 sccm. If degas in vacuum step is used instead of in-situ annealing, the degas is performed at a pressure between about 0.1 mT to about 50 mT, and at a temperature between about room temperature to about 450° C.
Next, a conformal dielectric liner 54 is deposited above and around pillars 132, resulting in the exemplary structure illustrated in
In an exemplary embodiment of this invention, dielectric liner 54 may be formed from boron nitride, such as described in commonly owned co-pending U.S. patent application Ser. No. 12/536,457, “A Memory Cell That Includes A Carbon-Based Memory Element And Methods Of Forming The Same,”filed Aug. 5, 2009 (Docket Number SD-MXA-335), which is incorporated by reference herein in its entirely for all purposes. Alternatively, dielectric sidewall liner 54 may be formed from other materials, such as SiN, SixCyNz, SixOyNz, SixByNz, (with low O content), where x, y and z are non-zero numbers resulting in stable compounds. Persons of ordinary skill in the art will understand that other dielectric materials may be used to form dielectric liner 54.
In one exemplary embodiment, a SiN dielectric sidewall liner 54 may be formed by PECVD using the process parameters listed in Table 1. Liner film thickness scales linearly with time. Other powers, temperatures, pressures, thicknesses and/or flow rates may be used.
With reference to
After pillars 132 have been formed, a dielectric layer 58b is deposited over pillars 132 to gapfill between pillars 132. For example, approximately 2000-7000 angstroms of silicon dioxide may be deposited and planarized using CMP or an etchback process to remove excess dielectric layer material 58b and dielectric hard mask layer 94 to form a planar surface 134, resulting in the structure illustrated in
With reference to
Conductive layer 140 may be formed from any suitable conductive material such as tungsten, another suitable metal, heavily doped semiconductor material, a conductive silicide, a conductive silicide-germanide, a conductive germanide, or the like deposited by PVD or any other any suitable method (e.g., CVD, etc.). In at least one embodiment, conductive layer 140 may comprise about 200 to about 2500 angstroms of tungsten. Other conductive layer materials and/or thicknesses may be used.
The deposited conductive layer 140 and barrier and/or adhesion layer 26 may be patterned and etched to form second conductors 22. In at least one embodiment, second conductors 22 are substantially parallel, substantially coplanar conductors that extend in a different direction than first conductors 20.
In other embodiments of the invention, second conductors 22 may be formed using a damascene process in which a dielectric layer is formed, patterned and etched to create openings or voids for conductors 22. The openings or voids may be filled with adhesion layer 26 and conductive layer 140 (and/or a conductive seed, conductive fill and/or barrier layer if needed). Adhesion layer 26 and conductive layer 140 then may be planarized to form a planar surface.
Following formation of second conductors 22, the resultant structure may be annealed to crystallize the deposited semiconductor material of diodes 14 (and/or to form silicide regions by reaction of the silicide-forming metal layer 52 with p+ region 14c). The lattice spacing of titanium silicide and cobalt silicide are close to that of silicon, and it appears that silicide layers 50 may serve as “crystallization templates” or “seeds” for adjacent deposited silicon as the deposited silicon crystallizes (e.g., silicide layer 50 enhances the crystalline structure of silicon diode 14 during annealing at temps of about 600-800° C.). Lower resistivity diode material thereby is provided. Similar results may be achieved for silicon-germanium alloy and/or germanium diodes.
Thus in at least one embodiment, a crystallization anneal may be performed for about 10 seconds to about 2 minutes in nitrogen at a temperature of about 600-800° C., and more preferably between about 650-750° C. Other annealing times, temperatures and/or environments may be used.
An alternative method of this invention uses a two-step ash process to remove photoresist without substantially damaging carbon layer 12. Referring now to
Referring now to
Next, photoresist regions 96 are used to pattern and etch metal layer 35, barrier layer 33, carbon layer 12, barrier layer 24, silicide-forming metal layer 52, diode layers 14a-14c, and barrier layer 28 to the top surface of dielectric layer 58a, to form substantially parallel pillars 132 having a width substantially equal to the width of conductors 20 below, as illustrated in
As a result of exposure to the etching process, photoresist regions 96 may develop a hardened crust on the surface of the material. In particular, photoresist exposed to a gas-phase plasma etching may develop a hardened crust composed of cross-linked organic polymer, and may contain small amounts of silicon or metal atoms. The surface crust may decrease the solubility of photoresist regions 96 and may increase the resistance of photoresist regions 96 to chemical removal. To overcome these problems, and also protect carbon layer 12 from damage, methods in accordance with this invention use a two-step ash process to remove photoresist regions 12.
Exemplary two-step ashing methods in accordance with this invention may use a microwave plasma generating reactor. Such a reactor may have a microwave source near the substrate, a parallel plate reactor with a microwave or radio frequency power source, or a reactor having a helical resonator. In some exemplary embodiments, the reactor is an inductively coupled plasma generating reactor.
In a first ashing step, water (“H2O”) and oxygen (“O2”) are primarily used in a downstream remote plasma (e.g., in which the substrate is located away from the plasma and/or not directly exposed to the plasma) to soften the hardened photoresist crust. In some embodiments, an additional processing gas, such as CxFy, x=1−4, y=2x, or y=(2x+2), may be used. Persons of ordinary skill in the art will understand that other gases may be used. Table 2 below describes an exemplary process window for the first step of the ashing process.
Other reactant gas species, flow rates, powers, pressures, temperatures and processing times may be used.
In a second ashing step, a directional in-situ radio-frequency (“RF”) generated oxygen-plasma (without remote plasma) is used to ash the photoresist. In particular, H2 is added, which may effectively reduce the photoresist ashing activation energy, without reducing the carbon layer 12 ashing activation energy. Therefore, the ashing rate of the photoresist is substantially independent of temperature, but the ashing rate of carbon layer 12 is temperature-dependent. As a result, by reducing the processing temperature, the ashing rate of photoresist regions 12 may remain substantially unchanged, whereas the ashing rate of carbon layer 12 may substantially decrease. In this regard, the directionality of the plasma may increase with reduced pressure. Both effects may reduce the undercut of carbon material on the sidewall of carbon layer 12.
Exemplary process parameters for the second ashing step, using O2 and H2, are provided in Table 3 below.
Other reactant gas species, flow rates, powers, pressures, temperatures and processing times may be used.
Alternative exemplary process parameters for the second ashing step, using N2 and H2, are provided in Table 4 below.
Other reactant gas species, flow rates, powers, pressures, temperatures and processing times may be used. The resulting structure after the two-step ash process is illustrated in
After the memory cell layers have been ashed, pillars 132 may be cleaned. In some embodiments, a dilute hydrofluoric/sulfuric acid clean is performed. Post-etch cleaning may be performed in any suitable cleaning tool, such as a Raider tool, available from Semitool of Kalispell, Mont. Exemplary post-etch cleaning may include using ultra-dilute sulfuric acid (e.g., about 1.5-1.8 wt %) for about 60 seconds and ultra-dilute HF acid (e.g., about 0.4-0.6 wt %) for about 60 seconds. Megasonics may or may not be used. Alternatively, H2SO4 may be used.
After pillars 132 have been cleaned, an in-situ anneal or degas in vacuum step may be performed. Carbon material tends to absorb moisture, especially during a wet clean process. This is problematic, because trapped moisture may result in de-lamination of carbon material and degradation in switching. In-situ annealing or degas in vacuum helps to drive out moisture before the next process step. In particular, the in-situ anneal or degas in vacuum is performed in the chamber of the next processing step. Degas in vacuum can also be performed in a transfer chamber or loadlock mounted on the same platform as that process chamber. For example, if the next processing step is formation of a sidewall liner, the in-situ anneal is performed in the chamber used to form the sidewall liner. The in-situ anneal may be performed at a temperature between about 200° C. and about 350° C., more generally between about 200° C. and about 450° C., for a duration between about 1 to about 2 minutes, more generally between about 30 seconds and about 5 minutes, at a pressure of between about 0.1 mT to about 10 T, more generally between about 0.1 mT to about 760 T. Alternatively, the in-situ anneal may be performed in an environment containing Ar, He, or N2, or a forming gas containing H2 and N2, at a flow rate of between about 1000 to about 8000 sccm, more generally between about 1000-20000 sccm. If degas in vacuum step is used instead of in-situ annealing, the degas is performed at a pressure between about 0.1 mT to about 50 mT, and at a temperature between about room temperature to about 450° C.
As illustrated in
After pillars 132 have been formed, a dielectric layer 58b is deposited over pillars 132 to gapfill between pillars 132. For example, approximately 2000-7000 angstroms of silicon dioxide may be deposited and planarized using CMP or an etchback process to remove excess dielectric layer material 58b to form a planar surface 134, resulting in the structure illustrated in
Next, second conductors 22 are formed above pillars 132, as described above in connection with
Persons of ordinary skill in the art will understand that alternative memory cells in accordance with this invention may be fabricated in other similar techniques. For example, memory cells may be formed that include reversible resistance switching element 12 below diode 14.
The foregoing description discloses only exemplary embodiments of the invention. Modifications of the above disclosed apparatus and methods which fall within the scope of the invention will be readily apparent to those of ordinary skill in the art. For instance, in any of the above embodiments, the carbon material may be located below the diodes 14. As stated, although the invention has been described primarily with reference to amorphous carbon, other carbon materials may be similarly used. Further, each carbon-based layer is preferably formed between two conducting layers such as titanium nitride or other barrier/adhesion layers to form a MIM stack in series with a steering element.
Accordingly, although the present invention has been disclosed in connection with exemplary embodiments thereof, it should be understood that other embodiments may fall within the spirit and scope of the invention, as defined by the following claims.
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/087,164, filed Aug. 7, 2008, “Methods And Apparatus For Forming Memory Cells Using Carbon Read Writable Materials,” which is hereby incorporated by reference herein in its entirety for all purposes.
| Number | Date | Country | |
|---|---|---|---|
| 61087164 | Aug 2008 | US |
