Non-volatile memory retains its stored data even when power is not present. This type of memory is used in a wide variety of electronic equipment, including digital cameras, portable audio players, wireless communication devices, personal digital assistants, and peripheral devices, as well as for storing firmware in computers and other devices.
Non-volatile memory technologies include flash memory, magnetoresistive random access memory (MRAM), phase change random access memory (PCRAM), and conductive bridging random access memory (CBRAM). Due to the great demand for non-volatile memory devices, researchers are continually improving non-volatile memory technology, and developing new types of non-volatile memory.
In accordance with an embodiment of the invention, a memory element includes a solid electrolyte layer that includes a matrix material having a metal dissolved therein, and a dopant distributed in the matrix material, the dopant competing with the metal to bind with elements of the matrix material at a crystallization temperature so that at least a portion of the metal in the matrix material remains unbound, to increase the temperature stability of the memory element.
In the drawings, like reference characters generally refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention. In the following description, various embodiments of the invention are described with reference to the following drawings, in which:
The scale of electronic devices is constantly being reduced. For memory devices, conventional technologies, such as flash memory and DRAM, which store information based on storage of electric charges, may reach their scaling limits in the foreseeable future. Additional characteristics of these technologies, such as the high switching voltages and limited number of read and write cycles of flash memory, or the limited duration of the storage of the charge state in DRAM, pose additional challenges. To address some of these issues, researchers are investigating memory technologies that do not use storage of an electrical charge to store information. One such technology is conductive bridging random access memory (CBRAM).
When a voltage is applied across the solid electrolyte block 106, a redox reaction is initiated that drives Ag+ ions out of the first electrode 102 into the solid electrolyte block 106 where they are reduced to Ag, thereby forming Ag rich clusters within the solid electrolyte block 106. The size and the number of Ag rich clusters within the solid electrolyte block 106 may be increased to such an extent that a conductive bridge 114 between the first electrode 102 and the second electrode 104 is formed.
As shown in
To determine the current memory state of the CBJ 100, a sensing current is routed through the CBJ 100. The sensing current encounters a high resistance if no conductive bridge 114 exists within the CBJ 100, and a low resistance when a conductive bridge 114 is present. A high resistance may, for example, represent “0”, while a low resistance represents “1”, or vice versa.
The solid electrolyte block 106 can include many materials, but the materials of greatest interest for use in CBRAM are the chalcogens, including oxygen (O), sulfur (S), and selenium (Se). Combining these with copper (Cu) or silver (Ag) yields binary electrolytes, such as Ag2Se or Cu2S. Alternatively, a transition metal, such as tungsten (W) can be reacted with oxygen to form a suitable base glass for an electrolyte. If, for example, the resulting tungsten oxide is sufficiently porous and in its trioxide form (WO3), silver or copper ions will be mobile within the material, and can form electrodeposits. Another approach is to combine chalcogens with other elements, such as germanium, to create a base glass into which Cu or Ag may be dissolved. An example of such an electrolyte is Ag dissolved in Ge30Se70 (e.g., Ag33Ge20Se47). This takes the form of a continuous glassy Ge2Se3 backbone and a dispersed Ag2Se phase, which is superionic and allows the electrolyte to exhibit superionic qualities. The nanostructure of this material, and of its sulphide counterpart, provide good characteristics for use in switching devices, such as CBRAM. The metal-rich phase is both an ion and an electron conductor, but the backbone material that separates each of these conducting regions is a good dielectric, so the overall resistance of the material prior to electrodeposition is high. Generally, a germanium selenide (GeSe) compound or germanium sulfide (GeS) compound is used in conventional CBRAM devices, but silicon selenide and silicon sulfide may also be used. Although the example embodiments of the invention below are generally described in terms of a GeS device, it will be understood that the principles of the invention may be employed in CBRAM devices that use GeSe, silicon selenide or sulfide, or other suitable solid electrolyte materials.
A solid electrolyte, such as those used in CBRAM, can be made to contain ions throughout its thickness. The ions nearest the electron-supplying cathode will move to its surface and be reduced first. Non-uniformities in the ion distribution and in the nano-topography of the electrode will promote localized deposition or nucleation. Even if multiple nuclei are formed, the one with the highest field and best ion supply will be favored for subsequent growth, extending out from the cathode as a single metallic nanowire. The electrodeposition of metal on the cathode physically extends the electrode into the electrolyte, which is possible in solid electrolytes, particularly if they are amorphous or partially amorphous, and are able to accommodate the growing electrodeposit in a void-rich, semi-flexible structure.
Because the electrodeposit is connected to the cathode, it can supply electrons for subsequent ion reduction. This permits the advancing electrodeposit to harvest ions from the electrolyte, plating them onto its surface to extend itself forward. Thus, in an electrolyte containing a sufficient percentage of metal ions, the growing electrodeposit is always adjacent to a significant source of ions, so the average distance each ion travels in order to be reduced is, at most, a few nm.
The resistivity of the electrodeposit is orders of magnitude lower than that of the surrounding electrolyte, so once the electrodeposit has grown from the cathode to the anode, forming a complete conductive bridge, the resistance of the structure drops considerably. The decreasing resistance of the structure due to the electrodeposition effect increases the current flowing through the device until the current limit of the source is reached. At this point, the voltage drop falls to the threshold for electrodeposition, and the process stops, yielding the final “on” resistance of the structure.
As noted above, the electrodeposition process is reversible by changing the polarity of the applied bias. If the electrodeposit is made positive with respect to the original oxidizable electrode, it becomes the new anode, and will dissolve via oxidation. During the dissolution of the conductive bridge, balance is maintained by electrodeposition of metal back into the place where the excess metal for the electrodeposition originated. The original growth process of the conductive bridge will have left a low ion density region in the electrolyte surrounding the electrode, and this “free volume” will favor redeposition without extended growth back into the electrolyte. Once the electrodeposit has been completely dissolved, the process will self-terminate, yielding the final “off” resistance of the structure. The asymmetry of the structure facilitates the cycling of the device between a high-resistance “off” state, and a low-resistance “on” state, permitting the device to operate as a switch or memory element.
In
In
To write to the memory cell, the word line 314 is used to select the cell 300, and a current on the bit line 308 is forced through the memory element 304, to form or remove a conductive bridge in the memory element 304, changing the resistance of the memory element 304. Similarly, when reading the cell 300, the word line 314 is used to select the cell 300, and the bit line 308 is used to apply a voltage across the memory element 304 to measure the resistance of the memory element 304.
The memory cell 300 may be referred to as a 1T1J cell, because it uses one transistor, and one memory junction (the memory element 304). Typically, a memory device will include an array of many such cells. It will be understood that other configurations for a 1T1J memory cell, or configurations other than a 1T1J configuration may be used with a CBRAM memory element such as is shown in
In the alternative configuration shown in
One challenge presented by the use of amorphous or partially amorphous solids such as GeS glasses in CBRAM devices is the poor temperature stability of such materials. In particular, these materials may start to change from an amorphous or partially amorphous phase to a crystal phase at temperatures as low as 250° C. to 280° C. In a crystal phase, the migration of ions in the material becomes more difficult, which can lead to failure of the memory device. The temperatures reached during the back-end-of-line (BEOL) CMOS process may be as high as 400° C., or higher. These temperatures are too high for the chalcogenide glasses that are used in conventional CBRAM devices. Attempts to improve the temperature stability of CBRAM devices by doping with oxygen have resulted in devices in which the Ag ions have insufficient ability to diffuse through the matrix, leading to devices that may be unable to retain an on-state.
One cause of this poor temperature stability in devices that use GeS is thought to be the presence of excess sulfur in the solid electrolyte. At higher temperatures, such as those found during a typical BEOL CMOS process, the amorphous GeS matrix, having a GeS1+x composition will increasingly form crystallization seeds in the form of a Ge/S lattice. The GeS2 phase is in this case less stable (Tmelting 515° C.) and more complex, and cannot be formed with regard to the GeS phase. Thus, sulfur becomes free, and increasingly binds with the Ag that has been dissolved into the glass. Depending on the Ag doping concentration and the amount of sulfur, AgS and GeS1+x can go into various compositions with each other. In the amorphous matrix, Ag exists in an unbound form, and in the form of AgS clusters. As the increased temperature leads to increasing amounts of free sulfur, the unbound Ag atoms will combine with the free sulfur to form AgS or Ag2S (at higher temperatures), which in turn can go into a common composition with GeS. This increasingly crystalline matrix, containing AgS/Ag2S clusters and compositions of AgxGeySz (in various compositions), requires increased switching voltages, so that switching of a memory element may no longer occur at the typical 0.2V programming voltage.
The optimal amount of sulfur in the layer for switching and temperature characteristics is difficult to determine, and difficult to control. Just as too much unbound sulfur may cause difficulties, as discussed above, so may too little sulfur. For example, in the case of an amorphous GeS matrix having a Ge to S ratio near 1:1, too little free unbound sulfur is available to permit sufficient formation of AgS clusters. Some formation of AgS clusters is desirable to facilitate switching, and insufficient sulfur to form such AgS clusters may result in poor switching characteristics.
In accordance with the invention, CBRAM having improved temperature stability may be provided by doping the solid electrolyte with an additional material that has the ability to bind sulfur in “competition” with Ag, so that excess sulfur is bound, while still permitting sufficient formation of AgS clusters. This can be achieved, for example, by doping with indium (In), tin (Sn), or antimony (Sb). Doping with such a material should cause the excess free sulfur to be bound (in part) to the doping atoms, and at higher temperatures should hinder the formation of additional Ag2-yS and the composition of Ag2-yS and GeS/S2 to a mixture phase of AgGeS. Additionally, these materials can go into common sulfur composition with Ge, to form, for example, GeSbS, reducing additional binding possibilities for Ag. Additionally, doping with such materials should have only minor effects on the switching characteristics of a CBRAM device, which should be substantially determined by the Ag/Ag+/AgS in the system, and only to a slight degree by the change in germanium, dopant, and sulfur compounds in the matrix.
Doping with Sb, Sn, or In is particularly effective in binding free sulfur at high temperature, since these dopants can bind at least 1.5 sulfur atoms. Sb, for example, can bind sulfur in an Sb2S3 configuration, or an Sb2S5 configuration at higher temperature. Thus, the excess formation of AgS clusters from free Ag atoms and the seed formation or crystallization of the AgGeS matrix is hindered. At lower temperatures, such as after cooling to Tr (room temperature) in a BEOL anneal process, the Sb2S5 configuration may no longer be stable, so that some reorganization of the sulfur may occur. However, at low temperatures (such as Tr), this will only result in low energetic agglomerations, which will not substantially affect switching of a CBRAM device.
The effects of doping with a material such as Sn, Sb, or In, in accordance with the invention, during an example CBRAM anneal process are illustrated in
In
While the example shown in
Referring now to
As described, the method starts with wafers onto which select transistors, vias, an isolation layer, and bottom electrode (typically containing W) have already been deposited using conventional techniques. Thus, the method described with reference to
In step 602, a GeS target, an Sb target, and an Ag target are installed in sputter equipment that is capable of using at least three sputter targets without disrupting the vacuum. Many commonly used sputter deposition devices, such as some of the models manufactured by Canon ANELVA Corporation, of Tokyo, Japan, KDF Electronics, of Rockleigh, N.J., and ULVAC Technologies, Inc., of Methuen, Mass. have this capability.
In step 604, a GeS layer is deposited. This layer may be deposited by means of RF-magnetron sputtering of a GeS-compound target, or other suitable sputtering techniques. In the case of RF-magnetron sputtering, typically Ar is used as a sputter gas, at a pressure of approximately 4.5×10−3 mbar and an HF-sputter power in the range of 1 to 2 kW. In some embodiments, this layer is deposited into pre-manufactured vias or on a W-plug of the memory element, and may have a thickness of approximately 40 to 45 nm, though a different thickness may be used.
In step 606, at the same time that the GeS layer is being deposited in step 604, the doping material for the GeS matrix is sputtered with a corresponding rate by means of co-sputtering from an Sb target. This can be done using, for example, DC sputtering with a power in the range of 500 W. Because this co-sputtering is occurring simultaneously with the sputtering of the GeS, the pressure is identical. Where Sb is used as the doping material, a concentration of Sb in the range of approximately 1% to approximately 5% is preferred, though other concentrations may be used.
In step 608, Ag is deposited on the Sb doped GeS layer, and in step 610, the Ag is diffused into the matrix by, for example, photodiffusion.
In step 612, the memory element is completed by depositing the Ag top electrode. This may be done, for example, by DC magnetron sputtering from an Ag target in a noble gas. In some embodiments, a TaN hard mask may then be deposited on the top electrode, and the CBRAM device may be completed using conventional techniques.
Referring to
In the cross section 700 shown in
In a device having a layout as shown in the cross section 700, the word line pitch and the bit line pitch may be equal, and may be approximately twice the feature size. Using a technology that provides a feature size of 90 nm, this means that the bit line and word line pitch would be approximately 180 nm.
In
Referring to
In
Next, as shown in
Referring now to
In step 904, information is stored in the conductive bridging memory element by reversibly forming a conductive bridge through the solid electrolyte layer, as described above.
Memory cells such as are described above may be used in memory devices that contain large numbers of such cells. These cells may, for example, be organized into an array of memory cells having numerous rows and columns of cells, each of which stores one or more bits of information. Memory devices of this sort may be used in a variety of applications or systems, such as the illustrative system shown in
The wireless communication device 1010 may include circuitry (not shown) for sending and receiving transmissions over a cellular telephone network, a WiFi wireless network, or other wireless communication network. It will be understood that the variety of input/output devices shown in
Memory cells formed in accordance with an embodiment of the invention may be used in a variety of memory devices. As shown in
As shown in
While the invention has been particularly shown and described with reference to specific embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is thus indicated by the appended claims and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced.