# Patent

## Title
Phase change memory cell in via array with self-aligned, self-converged bottom electrode and method for manufacturing

## Abstract

An array of “mushroom” style phase change memory cells is manufactured by forming a separation layer over an array of contacts, forming an isolation layer on the separation layer and forming an array of memory element openings in the isolation layer using a lithographic process. Etch masks are formed within the memory element openings by a process that compensates for variation in the size of the memory element openings that results from the lithographic process. The etch masks are used to etch through the separation layer to define an array of electrode openings. Electrode material is deposited within the electrode openings; and memory elements are formed within the memory element openings. The memory elements and bottom electrodes are self-aligned.

## Background
RELATED APPLICATIONS
This application is a divisional application of U.S. patent application Ser. No. 11/855,979 filed on 14 Sep. 2007, which application is incorporated herein by reference.


PARTIES TO A JOINT RESEARCH AGREEMENT
International Business Machines Corporation, a New York corporation; Macronix International Corporation, Ltd., a Taiwan corporation, and Infineon Technologies A.G., a German corporation, are parties to a Joint Research Agreement.
BACKGROUND
1. Field of the Invention
The present disclosure relates to high density memory devices based on programmable resistive materials, including phase change materials like chalcogenides, and to methods for manufacturing such devices.
2. Description of Related Art
Programmable resistive materials, including phase change based materials, have been used in nonvolatile random access memory cells. Phase change materials, such as chalcogenides, can be caused to change phase between an amorphous state and a crystalline state by application of electrical current at levels suitable for implementation in integrated circuits. The generally amorphous state is characterized by higher resistivity than the generally crystalline state, which can be readily sensed to indicate data.
Phase change materials are capable of being switched between a first structural state in which the material is in a generally amorphous solid phase, and a second structural state in which the material is in a generally crystalline solid phase in the active region of the cell. The term amorphous is used to refer to a relatively less ordered structure, more disordered than a single crystal, which has detectable characteristics such as higher electrical resistivity than the crystalline phase. The term crystalline is used to refer to a relatively more ordered structure, more ordered than in an amorphous structure, which has detectable characteristics such as lower electrical resistivity than the amorphous phase. Other material characteristics affected by the change between amorphous and crystalline phases include atomic order, free electron density and activation energy. The material may be switched into either different solid phases or mixtures of two or more solid phases, providing a gray scale between completely amorphous and completely crystalline states.
The change from the amorphous to the crystalline state is generally a lower current operation, requiring a current that is sufficient to raise the phase change material to a level between a phase transition temperature and a melting temperature. The change from crystalline to amorphous, referred to as reset herein, is generally a higher current operation, which includes a short high current density pulse to melt or breakdown the crystalline structure, after which the phase change material cools quickly, quenching the phase change process, allowing at least a portion of the phase change structure to stabilize in the amorphous state. It is desirable to minimize the magnitude of the reset current used to cause transition of phase change material from a crystalline state to an amorphous state. The magnitude of the needed reset current can be reduced by reducing the volume of the active region in the phase change material element in the cell. Techniques used to reduce the volume of the active region include reducing the contact area between electrodes and the phase change material, so that higher current densities are achieved in the active volume, with small absolute current values through the phase change material element.
One direction of development has been toward forming small pores in an integrated circuit structure, and using small quantities of programmable resistive material to fill the small pores. Patents illustrating development toward small pores include: Ovshinsky, “Multibit Single Cell Memory Element Having Tapered Contact,” U.S. Pat. No. 5,687,112, issued 11 Nov. 1997; Zahorik et al., “Method of Making Chalogenide [sic] Memory Device,” U.S. Pat. No. 5,789,277, issued 4 Aug. 1998; Doan et al., “Controllable Ovonic Phase-Change Semiconductor Memory Device and Methods of Fabricating the Same,” U.S. Pat. No. 6,150,253, issued 21 Nov. 2000.
Another memory cell structure under development, referred to sometimes as a “mushroom” cell because of the shape of the active region on the bottom electrode in a typical structure, is based on the formation of a small electrode in contact with a larger portion of phase change material, and then a usually larger electrode in contact with an opposite surface of the phase change material. Current flow from the small contact to the larger contact is used for reading, setting and resetting the memory cell. The small electrode concentrates the current density at the contact point, so that an active region in the phase change material is confined to a small volume near the contact point. See, for example, Ahn et al., “Highly reliable 50 nm contact cell technology for 256 Mb PRAM,” VLSI Technology 2005 Digest of Technical Papers, pages 98-99, 14 Jun. 2005; Denison, International publication No. WO2004/055916 A2, “Phase Change Memory and Method Therefore,” Publication Date: 1 Jul. 2004; and Song et al., United States Patent Application Publication No. US 2005/0263829 A1, “Semiconductor Devices Having Phase Change Memory Cells, Electronic Systems Employing the Same and Methods of Fabricating the Same,” published 1 Dec. 2005.
One prior art technique for making very small bottom electrodes, as described in the Ahn et al. publication, is referred to herein as a plug-in-via process, and includes forming a dielectric fill layer over circuitry for accessing the memory cell, etching vias in the dielectric fill layer to form an opening for making contact with the circuitry, and depositing electrode material into the via. The resulting structure is then planarized to expose the electrode material within the via. The phase change material is deposited and patterned in contact with the electrode. Although this technique is suitable for forming very small bottom electrode structures using a plug-in-via process, it has proved to suffer reliability and yield issues. For example, as described by Ahn et al., it has proven difficult to form reliable contact with the underlying access circuitry at the bottom of very small vias. This results in some cells in the array being permanently disconnected from the access circuits. See also, Horii, et al. “A Novel so Technology Using N-doped GeSbTe Films for Phase Change RAM,” 2003 Symposium on VLSI Technology, Digest of Technical Papers; Hwang, et al., “Full Integration and Reliability Evaluation of Phase-Change RAM Based on 0.24 um-CMOS Technologies,” 2003 Symposium on VLSI Technology, Digest of Technical Papers; Lai, et al., “OUM—180 nm Nonvolatile Memory Cell Element Technology for Stand Alone and Embedded Applications,” IEDM, 2001.
Furthermore, Ahn et al. have related that it is difficult to ensure in the plug-in-via process that the areas of the exposed tops of the plug electrodes are uniform after the planarizing step across a large array of such cells. Since the area of the top surface of the bottom electrode affects current density in the phase change material, and is a critical dimension for phase change cells of this type, variations in the contact area result in significant variations in operation of the cells in a single array.
Yet another problem arises in the formation of plug-in-via electrodes, because of the difficulty of uniformly filling vias. In particular, due to the dynamics of thin film deposition within small holes, the plug that results may include a void where the top of the via closes off before it has been completely filled below. Planarizing the structure may open the void, and create a hole in the top surface of the electrode plug. Such holes cause problems in the successful formation of a layer of phase change material over the electrode.
Another technology for making mushroom-type memory cells with pillar shaped bottom electrodes is described in our co-pending U.S. patent application Ser. No. 11/764,678; filed 18 Jun. 2007 (MXIC 1791-2).
Furthermore, the vias in the approach of Ahn et al. are made using lithographic processes which have characteristic minimum feature sizes, and typically result in vias that vary in diameter by as much as 5% of the minimum feature size. In some approaches, sidewalls are formed within the vias to reduce the cross-sectional area of the via used for electrode formation, reducing a critical dimension for the memory cell. The sidewall formation process involves conformal deposition of the sidewall material, having a uniform thickness around the walls of the via, and thus carrying the variation in size of the via into the critical dimension itself. Likewise, the pillars in the approach of U.S. patent application Ser. No. 11/764,678 are made by patterning photoresist using a lithographic process, and then trimming the photoresist elements in the pattern to reduce their dimensions below the minimum lithographic feature size. The trimmed photoresist element is used as an etch mask for formation of the bottom electrode and defines a critical dimension of the memory cell. This process also carries the variation in the minimum feature size of the photoresist elements into the critical dimension of the cell. Thus, for a lithographic minimum feature size of about 90 nm, which has a distribution of 5% across an array, the via diameters could vary as much as 4.5 nm. This 4.5 nm variation is carried according to the prior art techniques into the sub-lithographic feature size. So, a bottom electrode surface having a nominal diameter of 30 nm formed using the prior art techniques will vary in diameter across the array by as much as 4.5 nm, resulting in variation of the critical contact area of about 30% for a circular surface. This variation in the critical dimension of a programmable resistive memory cell reduces yield and complicates the technology for programming and reading the data in the cells.
Another problem with manufacturing very small dimension structures is alignment. When the structures are made using separate lithographic steps, the sizes of the structures, or of at least one of them, must be large enough to allow for alignment tolerances in the lithographic process. These requirements can restrict the flexibility in the design of the memory cells, and cause variation in the performance of the cells.
It is desirable therefore to provide a reliable method for manufacturing a memory cell structure with self-aligning and self-converging control over the critical dimensions of the bottom electrode and over the electrical integrity of connections to the bottom electrode, which will work with high density integrated circuit memory devices.
SUMMARY
A phase change memory device based on a “mushroom” type structure is described including a memory element with a self-aligned bottom electrode comprising a pillar of electrode material extending from a corresponding memory element that comprises a programmable resistive material, through a separation layer to contact corresponding contacts in access circuitry. The memory elements include programmable resistive material within corresponding vias, wherein the vias have bottom surfaces which have bottom surface areas and the pillars have top surfaces having surface areas substantially smaller than said bottom surface areas. Technology is described for manufacturing such devices in which the critical dimension of the area of contact between the memory element and the self-aligned bottom electrode converges within a small range across the array independent of the variations caused by lithographic processes, or other patterning processes, involved in manufacturing the device.
A manufacturing process for implementing the memory cell includes providing a substrate having an array of contacts where the contacts are coupled with access circuitry in the substrate. A separation layer is formed over the array of contacts, acting to separate the substrate from memory elements. The separation layer may comprise an etch stop material such as silicon nitride in a representative embodiment. Next, an isolation layer using a material such as silicon dioxide or similar material chosen for etching characteristics that differ from those of the separation layer is formed over the separation layer. An array of vias, termed memory element openings, is formed in the isolation layer using a lithographic process. The memory element openings are formed using a process which stops at the surface of or within the separation layer. Next, etch masks are formed within the memory element openings in the array, preferably using a process that compensates for variations in the diameters or widths of memory element openings in the array of memory element openings which result from the lithographic process. The etch masks are used during an etching process for forming bottom electrode openings in the separation layer which are self aligned with the memory element openings. Electrode material is deposited into the electrode openings to form an array of bottom electrodes contacting corresponding contacts in the array of contacts. Memory elements, comprising programmable resistive material such as the phase change material, are formed within the array of memory element openings over the array of bottom electrodes. Top electrodes are formed in contact with the memory elements.
Techniques are described for forming the etch masks using a process that compensates for variations in the array of memory element openings. One technique includes forming a sacrificial layer over the isolation layer, and the process of forming the memory element openings includes forming first upper opening segments within the sacrificial layer and second lower opening segments within the isolation layer. The first and second opening segments are formed so that they have first and second widths so that the sacrificial layer has an overhanging portion extending into the openings. Thus, the width of the opening in the sacrificial layer is less than the width of the opening in the isolation layer. A fill material, such as silicon, is deposited within the openings by a process causing formation of voids within the lower opening segments having width determined by the difference between the first and second widths. The fill material is anisotropically etched to open the voids, and then etched through the fill material at the bottom of the voids to expose the separation layer. In this manner, the exposed areas have widths substantially equal to the widths of the voids. The sidewalls of fill material on the sides of the lower opening segments define the etch masks. In this manner, the variation in the size of the openings defined by the etch masks depends on the dimension of the overhang, caused by the difference between the first and second widths. This dimension is independent of, and can be controlled over a range much less than, the variation in the size of the memory element openings caused by the lithographic process.
One alternative process described includes removing the etch masks from within the array of memory element openings after formation of the bottom electrode openings. Electrode material is deposited within the electrode openings and over the array of memory element openings. The electrode material is anisotropically etched to form side wall layers of electrode material within the memory element openings, leaving the bottom electrodes within the electrode openings. The side wall layers of electrode material are separated from the bottom electrodes to avoid shorts between the top and bottom electrodes. Programmable resistive material is deposited within the memory element openings over the bottom electrodes and in contact with the side wall layers of electrode material. The bit lines are formed over the programmable resistive material and in contact with the side wall layers of electrode material to provide a large area of top electrode contact with the programmable resistive material. According to this process, the side wall layers which are part of the top electrode structure, the memory elements comprising programmable resistive material, and the bottom electrodes are self-aligned.
In another alternative process, the electrode material is deposited within the electrode openings before removing the etch masks. The electrode material is anisotropically etched to form the bottom electrodes within the electrode openings, and the etch masks are removed from within the openings in the array of memory element openings. The programmable resistive material is deposited within the memory element openings over and in contact with the bottom electrodes. The bit lines, and optionally other top electrode structures, are formed over and in contact with the programmable resistive material to provide the top electrodes.
A memory device is described comprising an array of memory elements comprising programmable resistive material; an array of bottom electrodes, wherein said memory elements have a bottom surface which has a bottom surface area and the bottom electrodes have top surfaces in contact with and essentially centered on the bottom surfaces of respective memory elements, the top surfaces having surface areas substantially smaller than the bottom surface areas of the respective memory elements, and wherein the array of bottom electrodes is self-aligned with the array of memory elements; and top electrodes in contact with the memory elements in the array of memory elements in respective contact surface areas greater that the bottom surface areas.
A memory device is described herein comprising a substrate including an array of access devices having a corresponding array of contacts and a plurality of word lines coupled to the array of access devices. A separation layer overlies the substrate and the array of word lines. An array of bottom electrodes comprises pillars of electrode material through the separation layer contacting corresponding contacts in the array of contacts. An isolation layer over the separation layer includes an array of vias over corresponding bottom electrodes in the array of bottom electrodes, including programmable resistive material within the vias and in contact with the bottom electrodes. A plurality of bit lines in electrical communication with a programmable resistive material within the vias provides a current path from the bottom electrodes through corresponding elements of programmable resistive material to peripheral circuitry.
In technology described herein, the vias, and therefore the memory elements, in the array have respective widths that vary within a distribution that is determined by the lithographic process, or other patterning process, used to form them. The bottom electrodes in the array of bottom electrodes have widths that vary within another distribution that is independent of the patterning process used to form the vias. Thus, the width of a particular via in the array differs from the width of at least one other via in the array of vias by as much as 5% to 10% of the width of the particular via. In contrast, the width of the top surface of the bottom electrode in contact with the memory element within the particular via differs from the width of the top surface of the bottom electrode within the at least one other via by substantially less, such as by 5% to 10% of the overhang dimension, which is much less than said 5% to 10% of the width of the particular via.
Other aspects and advantages of the technology described herein can be understood with reference to the figures, the detailed description and the claims which follow.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of an integrated circuit device in accordance with an embodiment of the disclosure.
FIG. 2 is a partial schematic of a representative memory array as shown in FIG. 1.
FIG. 3A illustrates a cross-sectional view of a memory cell in accordance with an embodiment of the disclosure, having a self-aligned, centered bottom electrode.
FIG. 3B illustrates a plan view of the memory element and bottom electrode for a memory cell as shown in FIG. 3A.
FIG. 4 illustrates a cross-sectional view of a portion of an array of memory cells in accordance with an embodiment, showing a semiconductor substrate including access circuits.
FIGS. 5-15 illustrate stages in a fabrication sequence for a programmable resistance memory cell in accordance with a first method.
FIGS. 16-20 illustrate stages in a fabrication sequence for a programmable resistance memory cell in accordance with a second method.
FIG. 21 illustrates the compensation for variation in the sizes of features made using the lithographic process in formation of the critical dimension etch mask for the methods described herein.
FIG. 22 is a heuristic diagram of a memory array illustrating variations in the critical dimension among the selected memory cells.



DETAILED DESCRIPTION
Embodiments of the present invention are described with reference to FIGS. 1-22.
FIG. 1 is a simplified block diagram of an integrated circuit 10 including a memory array 11 implemented using phase change memory cells as described herein having self-aligned bottom electrodes with self-converged critical dimensions. A word line (or row) decoder 12 is coupled to, and in electrical communication with, a plurality of word lines 13, and arranged along rows in the memory array 11. A bit line (column) decoder 14 is coupled to and in electrical communication with a plurality of bit lines 15 arranged along columns in the memory array 11 for reading data from, and writing data to, the phase change memory cells in the memory array 11. Addresses are supplied on bus 16 to the word line decoder 12 and the bit line decoder 14. Sense amplifiers and data-in structures in block 17, including current sources for the read, set and reset modes, are coupled to the bit line decoder 14 via data bus 18. Data is supplied via the data-in line 19 from input/output ports on the integrated circuit 10 or from other data sources internal or external to the integrated circuit 10, to the data-in structures in block 17. In the illustrated embodiment, other circuitry 20 is included on the integrated circuit 10, such as a general purpose processor, special purpose application circuitry, or a combination of modules providing system-on-a-chip functionality supported by the phase change memory cell array. Data is supplied via the data-out line 21 from the sense amplifiers in block 17 to input/output ports on the integrated circuit 10, or to other data destinations internal or external to the integrated circuit 10.
A controller 22 implemented for example using a state machine, controls the application of bias arrangement supply voltages and current sources 23, such as read, program erase, erase verify, program verify voltages or currents for the word lines and bit lines, and controls the word line/source line operation using an access control process. The controller 22 can be implemented using special purpose logic circuitry as known in the art. In alternative embodiments, the controller 22 comprises a general purpose processor, which may be implemented on the same integrated circuit, which executes a computer program to control the operations of the device. In yet other embodiments, a combination of special-purpose logic circuitry and a general-purpose processor may be utilized for implementation of the controller 22.
As shown in FIG. 2, each of the memory cells of array 11 includes an access transistor (or other access device such as a diode), four of which are shown as 24, 25, 26, 27 and phase change elements 28, 29, 30, and 31. Sources of each of access transistors 24, 25, 26 and 27 are connected in common to a source line 32 that terminates in a source line termination 33. In other embodiments, the access transistors are replaced using diodes between the word lines and the memory cells. In another embodiment, the source lines of the select devices are not electrically connected, but are independently controllable. A plurality of word lines 13 including word lines 34 and 35 extend parallel along a first direction. The word lines 34 and 35 are in electrical communication with the word line decoder 12. The gates of access transistors 24 and 26 are connected to a common word line, such as the word line 34, and the gates of access transistors 25 and 27 are connected in common to the word line 35. A plurality of bit lines 15 including bit lines 36 and 37 are shown. The phase change element 28 is connected between the drain of access transistor 24 and the bit line 36, and the phase change element 29 is connected between the drain of access transistor 25 and the bit line 36. Similarly, the phase change element 30 is connected between the drain of access transistor 26 and the bit line 37, and the phase change element 31 is connected between the drain of access transistor 27 and the bit line 37. It should be noted that four memory cells are shown for convenience of discussion but, in practice, array 11 may comprise thousands to millions of such memory cells. Also, other array structures may be used.
FIG. 3A illustrates a cross-sectional view of a memory cell structure 38 with a self-aligned and self-converged critical dimension for the bottom electrode according to one embodiment. In addition, the bottom electrode is essentially centered on the bottom surface of the memory element 54. The memory cell structure 38 is formed on a substrate 39 including an array of contacts, such as contact 42 in an interlayer dielectric 43. A separation layer 49 comprising dielectric material with an array of bottom electrodes, including electrode 48, separates the array of contacts from overlying memory elements 54. The array of bottom electrodes is aligned with the array of contacts, such that the bottom electrode 48 is electrically connected to the contact 42. The contact 42 has a bottom surface that connects to an access device 45, such as a transistor or diode controlled by a word line, for coupling to a reference line. An isolation layer including dielectric, with an array of phase change memory elements, including element 54, overlies the separation layer 49, in alignment with the array of bottom electrodes. The memory elements (e.g. element 54) are formed within vias, referred to as memory element openings, in the dielectric material with which the bottom electrodes (e.g. electrode 48) are self-aligned as explained below. In the embodiment shown in FIG. 3A, the sidewalls of the vias are covered by the electrode material, forming conductive side wall layers 51. A bit line 41 overlies the array of memory elements, and contacts the conductive side wall layers 51 and the programmable resistive material in the vias. The bit line 41 is coupled to column select circuits 56 and so on as known in the art to complete the array.
In this embodiment, the bottom electrode 48 has a top surface that is recessed below a top surface of the separation layer 49. The programmable resistive material fills the recess and the via as illustrated. The extension of the programmable resistive material into the recess tends to locally increase the current density, and reduce the volume of the active region in the memory material. As can be seen by reference to FIG. 3A, the memory element has a bottom surface in contact with the separation layer 49 and the bottom electrode 48 having a bottom surface area, including the area within the recess, and the bottom electrode has a top surface, within the recess in this embodiment, having a surface area substantially smaller than said bottom surface area of the memory element. The bottom surface area of the memory element is largely determined by the process used to pattern the via, while the top surface area of the bottom electrode is defined by a process which compensates for variations in the process used to pattern the via, is self-aligned with the via and is centered within the via. Also, the top electrodes contact the memory elements in contact surface areas that are substantially greater than the bottom surface areas. The size of active region of the memory cell is largely determined by the small top surface area of the bottom electrode in contact with programmable resistive material.
Embodiments of the memory cell include phase change based memory materials, including chalcogenide based materials and other materials, for memory element 54. Chalcogens include any of the four elements oxygen (O), sulfur (S), selenium (Se), and tellurium (Te), forming part of group VI of the periodic table. Chalcogenides comprise compounds of a chalcogen with a more electropositive element or radical. Chalcogenide alloys comprise combinations of chalcogenides with other materials such as transition metals. A chalcogenide alloy usually contains one or more elements from column six of the periodic table of elements, such as germanium (Ge) and tin (Sn). Often, chalcogenide alloys include combinations including one or more of antimony (Sb), gallium (Ga), indium (In), and silver (Ag). Many phase change based memory materials have been described in technical literature, including alloys of: Ga/Sb, In/Sb, In/Se, Sb/Te, Ge/Te, Ge/Sb/Te, In/Sb/Te, Ga/Se/Te, Sn/Sb/Te, In/Sb/Ge, Ag/In/Sb/Te, Ge/Sn/Sb/Te, Ge/Sb/Se/Te and Te/Ge/Sb/S. In the family of Ge/Sb/Te alloys, a wide range of alloy compositions may be workable. The compositions can be characterized as TeaGebSb100−(a+b), where a and b represent atomic percentages that total 100% of the atoms of the constituent elements. One researcher has described the most useful alloys as having an average concentration of Te in the deposited materials well below 70%, typically below about 60% and ranged in general from as low as about 23% up to about 58% Te and most preferably about 48% to 58% Te. Concentrations of Ge were above about 5% and ranged from a low of about 8% to about 30% average in the material, remaining generally below 50%. Most preferably, concentrations of Ge ranged from about 8% to about 40%. The remainder of the principal constituent elements in this composition was Sb. (Ovshinsky '112 patent, cols 10-11.) Particular alloys evaluated by another researcher include Ge2Sb2Te5, GeSb2Te4 and GeSb4Te7. (Noboru Yamada, “Potential of Ge—Sb—Te Phase-Change Optical Disks for High-Data-Rate Recording”, SPIE v. 3109, pp. 28-37 (1997).) More generally, a transition metal such as chromium (Cr), iron (Fe), nickel (Ni), niobium (Nb), palladium (Pd), platinum (Pt) and mixtures or alloys thereof may be combined with Ge/Sb/Te to form a phase change alloy that has programmable resistive properties. Specific examples of memory materials that may be useful are given in Ovshinsky '112 at columns 11-13, which examples are hereby incorporated by reference.
Chalcogenides and other phase change materials are doped with impurities in some embodiments to modify conductivity, transition temperature, melting temperature, and other properties of memory elements using the doped chalcogenides. Representative impurities used for doping chalcogenides include nitrogen, silicon, oxygen, silicon dioxide, silicon nitride, copper, silver, gold, aluminum, aluminum oxide, tantalum, tantalum oxide, tantalum nitride, titanium and titanium oxide. See, e.g. U.S. Pat. No. 6,800,504, and U.S. Patent Application Publication No. US 2005/0029502.
Phase change materials can be changed from one phase state to another by application of electrical pulses. It has been observed that a shorter, higher amplitude pulse tends to change the phase change material to a generally amorphous state, and is referred to as a reset pulse. A longer, lower amplitude pulse tends to change the phase change material to a generally crystalline state, and is referred to as a program pulse. The energy in a shorter, higher amplitude pulse is high enough to melt the material in the active volume, and short enough to allow the material to solidify in the amorphous state. A program pulse has a magnitude sufficient to raise the temperature of the active region above a solid phase transition temperature, without melting. Appropriate profiles for pulses can be determined empirically, without undue experimentation, specifically adapted to a particular phase change material and device structure.
Representative chalcogenide material can be characterized as follows: GexSbyTez, where x:y:z=2:2:5. Other compositions can be used with x: 0 ̃5; y: 0 ̃5; z: 0 ̃10. GeSbTe with doping, such as N—, Si—, Ti—, or other element doping, may also be used. These materials can be formed by PVD sputtering or magnetron-sputtering with reactive gases of Ar, N2, and/or He, etc. and chalcogenide at the pressure of 1 mtorr ̃100 mtorr. The deposition is usually done at room temperature. A collimator with an aspect ratio of 1 ̃5 can be used to improve the fill-in performance. To improve the fill-in performance, the DC bias of several tens of volts to several hundreds of volts is also used. Also, the combination of DC bias and the collimator can be used simultaneously. The post deposition annealing treatment with vacuum or N2 ambient is sometimes needed to improve the crystallized state of chalcogenide material. The annealing temperature typically ranges 100° C. to 400° C. with an anneal time of less than 30 minutes.
The thickness of the chalcogenide material depends on the design of the cell structure. In general, a chalcogenide material with thickness of higher than 8 nm can have a phase change characterization such that the material exhibits at least two stable resistance states, although thinner layers may be suitable for some embodiments.
For memory cells implemented using GST or similar chalcogenides, suitable materials for implementing the bottom electrode and the conductive liner 51 in the illustrated embodiment include TiN, TaN, W and doped Si. Alternatively, the electrodes are TiAlN or TaAlN, or comprise, for further examples, one or more elements selected from the group consisting of Ti, W, Mo, Al, Ta, Cu, Pt, Ir, La, Ni, and Ru and alloys thereof.
A suitable material for implementing the isolation layer in the illustrated embodiment includes silicon dioxide SiO2. A suitable material for implementing the separation layer in the illustrated embodiment is silicon nitride. The materials for the separation and isolation layers are chosen for the differences in their etching characteristics, so that they can be selectively etched as described below.
FIG. 3B illustrates a simplified plan view of the memory cell structure 38 with the self-aligned, self-converged bottom electrode 48 according to one embodiment. The conductive liner 51 within the via, the programmable resistive material forming the memory element 54 within the conductive liner 51 and the top surface area of the bottom electrode 48 are shown. The top surface area of the bottom electrode 48 is represented in dashed lines to indicate that the bottom electrode 48 is positioned below the phase change material memory element 54. As illustrated, the memory element 54 is cylindrical, and has a diameter (also referred to a width) equal to F, which is preferably the minimum feature size for a lithographic process used to form the via. The bottom electrode 48 is pillar shaped, and has a circular top surface in this illustration that has a diameter (also referred to a width) equal to CD, which is a critical dimension for the memory cell. The bottom electrode 48 is essentially centered and self-aligned with the via as described below.
The dimension F varies over a range ΔF dependent on the lithographic and via etching processes used to form the via. The dimension CD is formed using a process that compensates for the variation in F, and therefore varies over a range that is substantially less than ΔF. The process that compensates for the variation in F causes self-convergence of the critical dimension CD to a small range ΔCD, improving the uniformity of operation of the array of memory cells, improving yield and simplifying the sensing and programming circuitry needed.
FIG. 4 is a cross-sectional view of a portion of an array of memory cells 57, 58 in accordance with an embodiment, illustrating access circuitry in a semiconductor substrate 59 coupled to an array of contacts 42 in the interlayer dielectric 43. Word lines 61, 62, and a source line 60 are formed within the interlayer dielectric 43. Doped regions 63, 64 in the semiconductor substrate 59 act as terminals of access transistors. Word lines 61, 62 over gate dielectrics act as gates for the access transistors, for coupling the contacts 42 to the common source line 60. In other embodiments the access circuits may be made using diodes instead of transistors, eliminating the need for word lines. Components of the memory cells 57 and 58 are given the same reference numerals as used in FIG. 3A.
A first method for manufacturing a memory cell as described herein is illustrated in FIGS. 5-15, showing structures of a single cell at various stages of the method, omitting the access circuits in the substrate for simplicity.
FIG. 5 illustrates a structure formed in a first stage of the manufacturing process, including deposition of the separation layer 46 of dielectric material, the isolation layer 47 of dielectric material, and a sacrificial upper layer 66 of dielectric material. In this embodiment, the sacrificial upper layer and the separation layer comprise silicon nitride, and the isolation layer comprises silicon dioxide. The materials of the layers are chosen for the ability to selectively etch as described below. Also, a lithographic process is used to form a mask 67 to define an array of openings over the contacts 42.
FIG. 6 illustrates a next stage in the process, in which opening 68 is formed on the structure using the mask 67. The opening 68 is formed by first etching through the sacrificial layer 66 using an etch chemistry suitable for the material of the sacrificial layer, forming an upper opening segment. Then a second etching step, or a continuation of the first etching step, if the etch processes can be shared, is used to etch through the isolation layer 47, stopping on or within the separation layer 46 before reaching the contact 42. The opening 68 extends through the sacrificial layer 66 and the isolation layer, exposing a top surface of the separation layer.
It is preferred that the width or diameter of opening 68 be close to the minimum feature size of the process used, typically a minimum lithographic feature size, to create the opening. Using conventional lithographic techniques, the width or diameter of opening 68 can be about 90 nm and will typically vary about 5% to 10%, which is about 4.5 nm to about 9 nm.
FIG. 7 illustrates a next stage in the process, in which the opening 68 is subjected to a selective undercutting etching process, such as applying dilute HF solution to slowly remove silicon dioxide in the isolation layer while leaving the silicon nitride sacrificial layer 66 and separation layer 46 intact. The opening 68 then includes an upper opening segment 73U having a first width 74 and a lower opening segment 73L having a second width 75. The size of overhang portion 72 is equal to half the difference between the widths 74 and 75, termed an overhang dimension 76. The overhang dimension 76 is determined by the selective etch process and can be very uniform across an array, and is not significantly affected by variations in the dimension F. (See discussion below referring to FIGS. 21 and 22.)
In an alternative process, the upper sacrificial layer comprises a material which can be selectively expanded to create the overhang. For example, using polysilicon for the upper sacrificial layer, oxidation of the structure of FIG. 6 causes growth of the overhang portion 72 while not effectively increasing the volume of the isolation layer 47 or the separation layer 46.
FIG. 8 shows a result of chemical vapor deposition of a fill material 77, such a amorphous silicon or other materials, using a process that grows the silicon layer at a substantially equal rate on the walls of the upper and lower opening segments 73U and 73L, resulting in the formation of a void 78 when the top of the opening closes before the interior is filled. Other materials chosen for their etch chemistry and the ability to grow conformal layers within high aspect ratio vias could also be used as the fill material 77. Also, other procedures, such as atomic layer deposition, physical vapor deposition, low-pressure chemical vapor deposition (LPCVD) or high density plasma chemical vapor deposition (HDPCVD) could be used to deposit the fill material 77, depending on the materials and geometries involved.
The fill deposition creates a self-aligned void 78 within the fill material 77 in the lower opening segment 73L. The lateral size or width of the void 78 is primarily controlled by the overhang dimension 76 and by variations in the deposition rates within the lower and upper opening segments 73L, 73U, independent of the lithographic process used to form the openings.
FIG. 9 shows the structure after etching the fill material 77 using an anisotropic etching process etching through the fill material 77 to open the void, and then continuing to etch until the separation layer is exposed in the region 69 below the void to form a sidewall spacer which acts as an etch mask 77a on the sides of the via. The mask 77a acts as an etch mask for subsequent steps, which has an opening dimension substantially determined by the dimensions of the void. The anisotropic etching also removes the sacrificial layer 66. Thus, the process used to form the etch mask compensates for variation in the dimension F of the via, as described above with reference to FIG. 8, and further explained with reference to FIGS. 21 and 22 below.
Next, another etching process etches through the separation layer 46 to a top surface 81 of the contact 42 to create a via (or a bottom electrode opening) 80. The via 80 is etched using anisotropic etching that aligns with the mask 77a. 
In FIG. 11, the mask 77a is removed by an etching process, such as wet etching using KOH or TMAH, to reopen the via, creating memory element opening 82 within the isolation layer 47, with the self-aligned electrode via 80 that is essentially centered within the memory element opening 82.
As illustrated in FIG. 12, an electrode material layer 83 is then deposited, by chemical vapor deposition for example, on the structure of FIG. 11 to fill the via 80, leaving a layer of electrode material over a portion of the top surface of the separation layer 46, within the memory element opening 82, along the inner sidewall of the memory element opening 82, and over a portion of the top surface of the isolation layer 47.
It is preferred that all or part of the portions of bottom electrode contacting the memory material member comprise an electrode material, such as TiN, or another conductor selected for compatibility with the phase change material. Other types of conductors can be used for the plug structures and the top and bottom electrodes structures, including for example aluminum and aluminum alloys, TiN, TaN, TiAlN or TaAlN. Other conductors that might be used comprise one or more elements selected from the group consisting of Ti, W, Mo, Al, Ta, Cu, Pt, Ir, La, Ni, Ru and O. TiN may be preferred because it makes good contact with GST (discussed above) as the memory material member; it is a common material used in semiconductor manufacturing; and it provides a good diffusion barrier at the higher temperatures at which GST transitions, typically in the 600-700° C. range.
FIG. 13 illustrates a next stage in the process, in which the electrode material layer 83 is selectively and anisotropically etched back, leaving electrode material to form the bottom electrode 84 within the bottom electrode via 80 in electrical contact with the contact 42 in the substrate. The process leaves a bottom electrode pillar and an electrode material liner 85 along the sidewall of the memory element opening 82. In the illustrated embodiment, the bottom electrode 84 in the bottom electrode via 80 is etched to form a recess 87 below the surface of the separation layer. Over-etching to form the recess helps insure that no electrode material short occurs between the bottom electrode 84 and the electrode material liner 85, and forms a recess to be filled by programmable resistive material aiding in providing a small active area for the memory cell. The diameter of the top surface of the pillar shaped bottom electrode can be controlled by the overhang etch process as described above. For example, in a particular embodiment, the diameter of the top surface of the bottom electrode can be controlled to be about 30 nm or less.
FIG. 14 illustrates a next stage in the process, after a phase change memory material member 88 (or other programmable resistive material) has been deposited into and filled the memory element opening 82 and the recess 87, and then has been planarized by a chemical mechanical polishing process, or otherwise. The phase change memory material member 88 extends into the recess 87, electrically contacting the bottom electrode 84, and fills memory element opening 82 within the isolation layer 47, electrically contacting the sidewall electrode material liner 85. The diameter (or width) 89 of the memory material member 88 will vary across the array by at least AF, as discussed above, and is substantially wider than the diameter 90 (or width) of the bottom electrode. This variation in the diameter of the phase change memory material within the memory cell has little effect on the set and reset characteristics of the cell, because the active region is determined to a much greater degree by the area of the contact with the bottom electrode.
FIG. 15 illustrates a next stage in the process in which a metal layer is patterned to define a bit line 91 that overlies the principal surface of the isolation layer 47. The bit line 91 is in contact with the sidewall electrode material liner 85 and the phase change memory material member 88, providing a large area of contact between the top electrode structure and the phase change memory material of the memory cell.
A second method for manufacturing a memory cell as described herein is illustrated with reference to FIGS. 16-20, where the second method includes steps leading to the structure of FIG. 10, and then, rather than removing the etch mask 77a as shown in FIG. 11, proceeds to deposit electrode material over the structure including the etch mask 77a as illustrated in FIG. 16. As illustrated in FIG. 16, an electrode material layer 92 is deposited by chemical vapor deposition, for example, on the structure of FIG. 10, to fill the bottom electrode via 80, over the sidewall etch mask 77a, and over the isolation layer 47.
FIG. 17 illustrates a next stage in the process, in which the electrode material layer 92 is selectively etched back removing the portions of the electrode material layer 92 over top surfaces of the isolation layer 47 and into the region within the opening defined by the etch mask 77a, leaving electrode material 93 within the separation layer 46 that functions as a bottom electrode.
FIG. 18 illustrates a next stage in the process, in which the etch mask 77a is removed by an etching process, such as wet etching using KOH or TMAH, to create a memory element opening 94 within the isolation layer 47.
FIG. 19 illustrates a next stage in the process, in which a memory material member 95 is deposited into the memory element opening 94, followed by a chemical mechanical polishing process. The memory material member 95 has a bottom surface in contact with the electrode material 93 and sides in contact with an inner surface of the isolation layer 47.
FIG. 20 illustrates a next stage in the process in which a metal layer is patterned to define a bit line 96. The bit line 96 has a bottom surface in contact with an upper surface of the memory material member 95, and overlies a principal surface of the isolation layer 47.
FIG. 21 is an expanded view of FIG. 8, referred to herein for the purpose of illustrating the self-aligned and self-converged nature of the process. A critical dimension of the memory cell structure 38 is the area of contact between the bottom electrode and the memory material. In this process, this critical dimension is determined by the diameter of the bottom electrode via 80 formed using the etch mask 77a, shown in FIG. 9. In turn, the diameter of the etch mask 77a is determined by the size of the void 78 shown in FIG. 21. The size of the void is determined in this process by the overhang dimension O, formed (in one embodiment) by selective etching of the isolation layer 47 to undercut the sacrificial layer 66. In the illustration, the dimension 2X is equal to the dimension F labeled in FIG. 6, and varies over a range equal to F+ΔF, as discussed above. The dimension O also varies by a range of O+ΔO. Because the undercut etch can be controlled sufficiently that ΔO is much less than ΔF, and is essentially independent of the variations in F, the process of forming the void compensates for the variation in F.
The manner in which the process compensates for variations in F can be understood as follows. The fill material is deposited using a substantially conformal deposition process, so that it is deposited on the sidewalls within the lower opening segment 73L in FIG. 7 through the isolation layer at about the same rate as it is deposited on the sidewalls within the upper opening segment 73U in FIG. 7, through the sacrificial layer. Thus, when the thickness X of the fill material reaches one half the width (2X=F+ΔF) of the opening in the sacrificial layer, there remains a void 78 between the sidewalls of fill material growing in the isolation layer. Since the opening is closed at the top, no more growth is possible within the lower opening segment through the isolation layer, and the void 78 is established. The fill deposition process is executed so that the openings in all cells are closed, and therefore the thickness X of the deposited material at which the top is closed varies with the variations in F. However, the size CD of the voids in all the cells remains equal to 2(O+ΔO), independent of and compensating for variations in F.
FIG. 22 is a heuristic diagram of a memory device comprising an array of memory cells, illustrating a feature of an array of memory cells made as described herein. In particular, an array including millions of cells covers a relatively large area on a device, over which the lithographically formed vias will vary in size over a range ΔF, as discussed above. Therefore, if one samples a memory cell 119 in a first sector 120 of the array, and compares that cell with a memory cell 121 is a second sector 122 of the array, it is likely that the via used for formation of the memory element will differ by as much as ΔF. However, the width of the surface of the bottom electrode in contact with the memory element, in embodiments of the present invention will vary by at most 2ΔO.
For example, using a lithographic process resulting in a 90 nm feature size, varying by 5% across the array, the width F of a memory element varies by about 4.5 nm across an array. The overhang dimension 76, which is determined by the undercut etch process or by the overhang growth process, may also vary across an array by 5%. As explained above, in order to make a 40 nm CD, the overhang dimension 76 should be 20 nm. If the process creating the overhang results in a variation of 5%, then the overhang dimension O could vary by 1 nm on each side. This would result in a variation in CD of 2 nm for the nominally 40 nm hole across an array, or 5%. This 2 nm variation is substantially less than the variation in the lithographic dimension. In contrast, prior art sidewall spacer techniques that do not compensate for lithographic variations would result in a 4.5 nm variation across the array for the nominally 40 nm hole, or 11.25%. The self-converging process described herein substantially narrows the distribution of CD across the array.
Thus, for an illustrative example in which the dimension F is assumed to vary across the specified range of about 5% for nominally F=90 nm and the dimension CD is assumed to vary across a range of about 5% for nominally CD=40 nm, the cell 119 may have a width of dimension F of about 92 nm and a dimension CD of about 39 nm, while the cell 121 may have a width of dimension F of about 88 nm, and a dimension CD of about 41 nm. Thus, a novel structure results in which the width of the memory element in cell 119 as measured varies from the width of the memory element in cell 121 by 4/92, or 4.3% of the width F in cell 119, in the example illustrated. However, the width of the critical dimension in cell 119 varies from that in cell 121 by 2/92, or 2.2% of the width F in cell 119. Therefore the critical dimensions of the sampled memory cells vary by less than the variations in the width of the memory elements in a way not possible in the prior art.
While the present invention is disclosed by reference to the preferred embodiments and examples detailed above, it is to be understood that these examples are intended in an illustrative rather than in a limiting sense. It is contemplated that modifications and combinations will occur to those skilled in the art, which modifications and combinations will be within the spirit of the disclosure and the scope of the following claims.

## Claims

1. A memory device, comprising:
an array of memory elements comprising programmable resistive material;
an array of bottom electrodes, wherein said memory elements have bottom surfaces which have bottom surface areas, and the bottom electrodes have top surfaces in contact with and essentially centered on the bottom surfaces of respective memory elements, the top surfaces of the bottom electrodes having surface areas substantially smaller than the bottom surface areas of the respective memory elements, and wherein the array of bottom electrodes is self-aligned with the array of memory elements; and
top electrodes in contact with the memory elements in the array of memory elements, wherein the memory elements in the array of memory elements comprise programmable resistive material within respective memory cell vias through an insulating layer, and wherein the top electrodes comprise respective conductive side wall layers surrounding and directly contacting the programmable resistive material within the memory cell vias.

2. The memory device of claim 1, wherein the side wall layers of the top electrodes are self-aligned with the array of memory elements.

3. The memory device of claim 1, wherein
the memory cell vias have respective widths that vary within a distribution across the array of memory elements,
the bottom electrodes in the array of bottom electrodes have widths that vary within another smaller distribution,
the width of a particular memory cell via over a particular bottom electrode differs from the width of at least one other memory cell via over another bottom electrode by a measured percentage of the width of the particular via; and
the width of the particular bottom electrode differs from the width of said another bottom electrode by substantially less than said measured percentage of the width of the particular memory cell via.

4. The memory device of claim 1, wherein the top electrodes have contact surface areas in contact with the memory elements substantially greater than the surface areas of the top surfaces of the bottom electrodes.

5. A memory device, comprising:
a bottom electrode;
a memory material in contact with the bottom electrode;
a conductive element in direct physical contact with the sidewall of the memory material; and
a top electrode in direct physical contact with both the memory material and the conductive element.