Programmable Metallization Cell

Presented by: Aditi Gaur, Nupur Bihari, Ashish Mittal Bharati Vidyapeeth College of Engineering Electronics and Telecommunication

Programmable Metallization Cell

7. Summary

Abstract
The programmable metallization cell, or PMC, is the latest form of non-volatile computer memory being developed to replace the widely used flash memory, providing a combination of longer lifetime, lower power, and much enhanced memory density. This paper lucidly illustrates the fabrication process and principle of operation of PMC devices. PMC uses a system of storage where instead of electrons (as in traditional electronics), the ions themselves are moved. Instead of storing bits as an electronic charge, the technology creates nanowires from copper atoms the size of a virus to record binary ones and zeros. This has given rise to a new field called nanoionics which has innumerable applications and the potential to radically change the way we store data.

8. Bibliography

Overview
Programmable Metallization Cell memory (PMCm) is a simple and elegant form of storage that represents a radical departure from all existing and developing technology in this field. It utilizes the internal properties of elements, and their solid state chemistry to develop a structure which can act as a durable form of non-volatile storage. It uses a system which works on varying the resistance of a structure at very low levels of voltage and energy. These energy levels are so low (to the tune of 1pJ) that they were considered unattainable till a few years back. The major advantage of PMC is that the method of fabrication is compatible with the technology used to create the smallest of transistors. The mechanism behind the memory behavior is a little known feature of certain materials. In amorphous state, they can incorporate very large amounts of metal and behave as solid electrolytes. A thin amorphous film is made with two metal contacts, which under suitable bias conditions, is capable of forming a reversible pathway to facilitate the flow of ions, as opposed to conventional electronics which uses electron movement for passage of current. When the voltage is reversed, the

Contents
1. Overview
2. Principle of Operation

3. Fabrication Techniques 4. Characteristics 5. Key Benefits 6. Strategic Impact

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material easily goes back to its amorphous state. Recent advances in the field of barrier metallurgy (which allows hitherto unacceptable combinations of metal to be used in integrated circuits), an improved understanding of solid state ionics and a universal demand for better and more advanced battery performance have helped in development of this new technology which is a radically new concept with the potential to completely change the face of data storage.

b) if oxidizable metal is exhausted Solid electrolyte can be made by organic as well as inorganic elements. However particular interest lies in the elements headed by oxygen in periodic table referred to as CHALCOGENS. Typical focus is on elements making thermally stable compounds like oxygen (O), sulphur (S), and selenium (Se). Solid electrolytes can be formed in a variety of ways. For example, a) Combination of chalcogens with silver (Ag) or copper (Cu) which yields "binary" electrolytes like Ag 2Se or Cu2S. b) Another way is to combine chalcogens with germanium to create base glass in which Cu or Ag can be dissolved. This is a ternary electrolyte Ge30 Se70 (Ag33 Ge20 Se47 ). It takes the form of continuous glassy backbone in which dispersed nanoscale Ag 2Se phase exists in super ionic phase. It exhibits ideal switching characteristics. The metal rich phase is both an ion and an electron conductor but is separated by a backbone material acting as dielectric. Hence its resistance is high, prior to electrodeposition. Solid electrolyte is made to contain ions throughout its thickness. The ions nearest to reducing cathode will reduce first. Ions removed from the electrolyte are quickly replaced by the ion current from oxidizable anode. Non uniformity in ion distribution will promote localized deposition. This deposition extends cathode into the electrolyte as a single metallic nanowire. However the ion entering from the anode does not have to travel the entire length of the electrolyte to reach cathode.
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Principle of Operation
Solid electrolytes behave similar to liquid electrolytes. In solid electrolytes containing metal ions, only positive ions are mobile while the negative counter ions are fixed. Anode contains oxidizable metal (for example, Cu or Ag) and cathode contains an inert electrode (like tungsten). Electrolyte is solid acting as a dielectric. A voltage as low as a few hundred mV will reduce ions to form metal atoms at the cathode and put ions into electrolyte via oxidation, at the anode. If oxidation and reduction processes are in balance then charge neutrality will be maintained else charge will build up and it will halt the electrodeposition process. Now, the electrodeposition process cannot continue if the oxidizable metal is made negative w.r.t. the inert cathode. This condition is called REVERSE BIAS and it will work in exactly the opposite manner. The electrodeposition will stop in 2 cases: a) if the potential drops below the level required to stimulate electrodeposition

The subsequent ion will just fill up the next vacated space and all ions will do the same until the last ion has filled the vacated space closest to the anode. So the ions harvest themselves from the electrolyte plating itself onto the surface as it extends forward. The electrodeposit is always adjacent to a significant number of metal ions in the electrolyte, so the average distance each ion has to travel is at most few nm. This is shows coordinated motion of ions. This intrusion of nanowire is possible in electrolytes particularly if they are glassy in nature, since they are void-rich and flexible and are able to accommodate the growing nanowire.

the threshold of the electrodeposition is lower than the write voltage because the voltage required to sustain an electrodeposition is lower once deposition has started. As said earlier, this process is reversible in nature by reversing the polarity applied. When electrodeposit is made positive w.r.t. oxidizable anode, it acts as the new anode. As the pathway created earlier is now dissolved, balance is essentially maintained by electrodeposition of metal back onto the place where the excess metal came in the first place. Original growth process leaves a low density region at the anode and this will favor the redeposition without any excess growth. The process is self-terminating and the system hence reverts into a state of high resistance. Asymmetry of the structure allows the cycling of the devices from high resistance (off state) to low resistance (on state), therefore allowing them to be used in high endurance memory and switching operations. The information is stored by reducing the metal at cathode obtained by oxidation at the anode, and storing it as an electrodeposit. It is important to be noted that the information is stored via metal deposition and not charge storage. Hence it shows high retention characteristics. Ion mobility is as high as 10-3 cm2/V.s and internal field around 105V/cm. Hence the electrodeposit growth rates are of 1nm/nsec. The erasing of data can also be done by applying reverse bias which decreases the concentration by oxidizing the deposit and removes the excess metal as ions migrate away to the electrolyte or the positive electrode. Reading of the data is done by detecting the amount of reduced metal deposited at the electrolyte. It requires a
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Figure 1. Formation of a metallic nanowire extending from the cathode

After the growth of electrodeposit, the resistivity of the entire structure drops indicating that the writing process is complete. Decrease in resistance causes the current to increase until the current limit of the source is reached. At this level the voltage drop falls to the level of threshold voltage for electrodeposition, and the process stops, yielding the final structure. However

small control transistor to be switched on, and a small voltage to be applied across the cell. If there is a nanowire present, indicating lower resistance and higher current, it is read as one (1). Similarly if the nanowire is not present, it indicates higher resistance and lower current and it is read as a zero (0).

2. Solid electrolyte 3. Oxidizable electrode metal layer as top

Fabrication Techniques
The PMC device can be fabricated in two different ways: Using Chalcogenide-based electrolytes Using Oxide-based electrolytes The basic structure of a Chalcogenide-based PMC is as shown:

The 2 electrodes are separated by a dielectric medium. This insulating layer defines the area of electrolyte that touches the bottom electrode. Here, the diameter D creates a pit which is formed due to electrodeposition, which in turn results in reduction of resistance between the electrodes. In chalcogenide-based devices tungsten is generally used as an inert electrode, i.e., the bottom layer, but many electrochemically indifferent materials can be used, such as nickel (Ni) which are generally used in nanodevices. The dielectrics used are of two types:Deposited silicon dioxide for devices with D>100 nm Spincast poly-methylmethacrylate (PMMA) for D<100 nm Generally PMMA is preferred as a dielectric because it can be patterned directly by using standard electron beam lithography (EBL).Finally top electrode is capped with gold to prevent tarnishing of silver. This device is fabricated using electron beam exposure using PMMA dielectric and nickel film.

Figure 2. PMC structure showing main layers with PMMA dielectric

As the diagram illustrates, this PMC consists of 3 layers: 1. Inert electrode as bottom layer
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The oxide method of fabrication involves depositing a tungsten layer using the process of chemical vapour deposition (CVD) on silicon dioxide substrates. The vias (pathways) are defined by optical lithography and dry etching. The exposed tungsten is oxidized, thus creating a base glass layer on

the W electrode. Ag or Cu layers are then deposited on top of this. In this kind of a structure, the WO3 electrolyte is present only at the base of the via. Although PMC devices can be easily manufactured using the above mentioned methods, one critical disadvantage is that the silver-doped germanium selenide materials do not readily tolerate processing conditions at temperatures beyond 200C. This means that the back-end-of-line (BEOL) processing for integration with CMOS will have to be done at comparatively lower temperatures. This increases the cost of the device. To overcome this problem, silver-doped germanium sulphide solid electrolytes are used. These materials have excellent thermal stability and are able to withstand the high temperatures used in BEOL processes. However, copper doping is easier to implement since the metal is already widely in use for interconnecting IC circuitry. The fabrication process involves diffusing the mobile metal ions into a chalcogen-rich base glass using the process of photodissolution. A tungsten layer is deposited on the silicon dioxide layer using the process of chemical vapour deposition. A few paths (called vias) are made in this dielectric using optical projection lithography and reactive ion etching. Ag or Cu is then dissolved into the base glass using photodissolution at room temperature using ultra-violet light. After this, an additional 50nm of Ag or Cu is added to ensure a continuous oxidizable source for electrodeposition. Furthermore, this layer acts as the top electrode. Through experiments involving annealing it was revealed that the Ag based devices show
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optimum performance even during harsh temperature conditions. Cu does not survive these temperature ranges (300 to 430C) since it is a reactive metal.

Figure 3. Schematic diagram of test device layout.

Characteristics of PMC
To obtain characteristics we use voltage sweep technique. This means periodically varying voltage is applied to electrodes to get the electrodeposition that is a function of voltage. Since electrodeposition governs the resistance of the device, we can plot I-V characteristics. The voltage sweep is done by applying the maximum reverse bias, varying through zero to an appropriate forward voltage, and sweeping back again through zero. This plot shows single current voltage characteristics for Ag-Se-Ge electrolyte, with voltage sweep from -1V to +0.5V to -1.0V.

Fig 4. Current-voltage plot of a device with Ag-GeSe electrolyte with 1A current limit.

The device switches from off state resistance to an on state resistance at 0.24 volts. As stated earlier, once electrodeposition is initiated, the threshold for further deposit decreases. Now we show the resistance voltage characteristics for this device. Resistance in on state is dependent on programming current. This is because as long as sufficient voltage is maintained for the electrodeposition to persist, the reduction of silver/copper ions will go on and resistance of the conducting bridge will continue to fall even after the bridge has been formed. However if the current source is limited, once the voltage drops below the level required to sustain deposition, the process ceases. And the resistance between electrodes remains constant. This resistance is the closed resistance of the devices.

Fig 5. Resistance voltage plot of the same device. Off resistance is in excess of 1G over voltage range shown and the on resistance is over 4 orders of magnitude lower.

Appearance of low threshold is typical of all PMC devices. Germanium sulphide based electrolytes have very similar characteristics to their selenide based counterparts. But sulphide based devices are able to withstand higher temperatures than selenium devices. Moreover the off resistances are more than an order of magnitude higher for the devices of same diameter and electrodeposit , and the erase thresholds are much higher too. For the oxidizable metal we can either use silver or copper. Research is still going on the response of copper at high temperatures because of its reactivity. This graph shows the off and on state resistances at the operating temperature.

Key Advantages
The unique attributes of PMC make it an attractive component where memory and storage of data in the near future is concerned.
1. Operation at low voltages: PMC

.
Fig 6. Resistance versus operating temperature.

These devices show excellent speed in cycling operations. This helps the device to be useful in high-speed switching applications as well.

memory operates at voltages lower than 0.3 V. Not only does this ensure that unnecessary wastage of energy is reduced, but also guarantees its applications in a variety of systems.

2. High

speed write and erase operations: Write and erase operations at speeds less than 30ns will make sure that the clock rate is extremely high and will pave the path for development of highly efficient and fast computers.

3. Low energy to change state: Low

Fig 7. Response to cycling using train of positive and negative pulses. Output waveform is the voltage drop across a series resistor.

Hence we can say that sulphide based devices are suitable for use in PMC and that Ag doped materials will survive back-end-of-line processing to 430C. Copper, a material which has widespread application in the semiconductor industry, is an appropriate substitute for silver in sulphide based devices.
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energies to the tune of less than 1pJ are required to change the state of the memory from zero to one or vice versa. This will help in exponential growth of appliances that operate on minimum required energy, less heat dissipation and thus higher efficiency.

4. Scalability: Moores Law, which

defines the reduction in dimensions of transistors, can also be applied in case of PMC since their fabrication technologies (w.r.t. size) are

compatible. In small devices like the transistors that are in use today, the major problem faced is that of heat dissipation. Although with advancement in technology, the supply voltage of these components is being reduced, thus leading to lower heating, it is impractical to think of a transistor that will work below 0.6 V. However, PMC does not face this limitation. The electrochemical dissolution process which is used in a PMC device operates at potentials below 0.5V so scalability requirement for future technology is satisfied. In this respect, PMC is unique among all the future memory contenders. Other benefits come from scalability of other performance measures such as speed and power.

dielectric layers. By substituting an amorphous layer for a metal plug, we can create a PMC or a selectively switchable connection between metal layers. This can either be used to configure the logic design or as part of a local memory array where the transistors in the underlying silicon provide the drive and sense circuitry. This small change incorporated in the design will dramatically reduce the cost and leverage the rapid advances that have been made in mainstream silicon processing but at the same time offer a radically new system.

6. Operation as a low refresh-rate

5. Easy integration with IC logic

circuitry: A number of PMC memory chips can be put on a single IC due to their small size. Not only does this help in miniaturization of devices, but also opens up new avenues of research in hitherto unknown fields like ULSI (Ultra Large Scale Integration). Also, it is an effective way of bringing the cost of the device down. Todays computer chips use very dense arrays of logic transistors. Barrier layers are introduced so that good conductors like silver or copper can be used. These metal layers also have to be coupled selectively using metal plugs that fill small voids in the inter-metal
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DRAM or as a true non-volatile memory with high endurance (based on the programming mode): PMC memory is very versatile and can be programmed to be used as a DRAM (Dynamic Random Access Memory). DRAM stores each bit of data in a separate capacitor within an integrated circuit. Since the charge leaks from capacitors, they have to be continually refreshed in order to store the data. When a PMC is used for this application, it can be programmed to store the bits in the form of nanowires, leading to lower refresh rates required for optimum utilization. Also, it can be used as a true non volatile memory that would suffice as permanent storage. Thus, because of its varied applications, PMC not only has the potential to replace Flash

memory, but also present-day RAM and ROM.

Strategic Impact
Although Moores Law predicts steady advancement in technology leading to reduction in size of transistor, this is not affected in reality. Productivity in circuit design lags behind so although we may be able to envision chips with billions of logic transistors, limited design resources will restrict us to much modest capabilities. One solution to the problem is to add more memory and reuse existing designs. This is definitely a pragmatic approach but greatly reduces the scope for development of newer and more efficient technology. The memory technologies used today, DRAM for core memory and Flash as non volatile storage, are rapidly running out of steam; DRAM, because of its energy requirement where refresh rates are concerned, and Flash because of the steady reduction in supply voltages when device programmability rests on a high-voltage, quasi-breakdown process. Also, DRAM requires new dielectric materials to allow charge to be stored in smaller areas. Neither technology faces abrupt cut-offs currently, but as the storage requirement increases, and higher speed is needed, we will need devices with superior performance. Newer memory technologies like FeRAM and MRAM face even greater material issues than DRAM and are thus not very viable for future use. PMC uses a simple but radically different concept, making it capable of changing the face of conventional technology. Thus, manufacturing is made easy and the
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flexibility in applications that comes from having one high density memory cell will ensure that it is used for both dynamic and non-volatile applications. The market for electronic components is at a point where computing, data management and office operations are well defined and will continue to evolve. We now have much higher levels of integration in prospect that will demand a better system for design and continuous upgrading. Many new applications such as image and voice recognition, security systems, highly configurable networks and vastly increased portability are on the scene. For all these designs the very basic requirement is massive processing power, which needs to be backed by very large memories. A universal solid state memory is fast, operates at very low voltages, is fully integratable with future logic and has low cost per bit ratio. Not only is it technically sound, but also very economically viable. Thus a transition to PMC memory would not only ensure unification in the kind of technology required for storage but will also help in keeping the cost of the device down.

Summary
We have explained in this paper, the technology behind programmable metallization cell. Since this device is using nanoscale links resulting in low/high resistance, we can understand that the size of this entire device will be shrunk down to nanoscale dimensions without compromising on operating conditions. Thus physical

scalability, combined with low voltage and current operations suggests that extremely high storage densities will be possible. Also charge required to switch a PMC element to a low resistance state is comparable to or lower than the charge required for each refresh cycle of a DRAM. Primary solid state non-volatile memory in use today is Flash memory. It uses a floating gate concept, which requires large current to be rewritten. Since each current application physically degrades the cell, such a cell will eventually be unwritable. Moreover charge leakage is also a major problem with floating gate in the flash memory. As we have already seen, PMC does away with most of these disadvantages. Its writing process is almost infinitely reversible. Simplicity of the layout and its working makes PMC as the most universally applicable memory so far.

4. PMC Non-Volatile Memory, Axon technologies Corp.

5. http://www.pcworld.com/article/1390

81/days_may_be_numbered_for_flas h_memory.html

Bibliography
1. Non-Volatile Memory Based on Solid Electrolytes, Michael N. Kozicki, Chakravarthy Gopalan, Murali Balakrishnan, Mira Park, and Maria Mitkova 2. Programmable Metallization Cell Memory Based on Ag-Ge-S and CuGe-S Solid Electrolytes, M.N. Kozicki, M. Balakrishnan, C. Gopalan, C. Ratnakumar, and M. Mitkova 3. Silver incorporation in GeSe glasses used in programmable metallization cell devices, M. Mitkova, M.N. Kozicki

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