1 2012EE50545, Digital Electronic Circuits, I semester 2013-2014, IIT Delhi

Implementation of Molecular Memories Using Porphyrin-based Polymers

Ashish Kumar, Sophomore Undergraduate, Electrical Engineering, IIT Delhi
AbstractData storage devices use either electronic or magnetic memory cells. The use of individual molecules as data storage elements could transform the data storage picture completely as molecular memories lead to a thousand-fold reduction in size. This paper describes the use of porphyrinbased polymers as an approach to molecular memories and how this can potentially lead to smaller and cheaper integrated circuits. Index Terms Porphyrin. Electric Charge, Molecular Memories,

harnessed to read and write data. Section IV sums up the discussion and talks about further areas which can be exploited on the quest to achieve greater miniaturization of electronic devices as we see them today. II. PORPHYRIN Porphyrins are derived from porphin (sometimes spelled porphine), an organic compound that is aromatic and

I.

INTRODUCTION

OLECULAR MEMORY refers to a data storage technology that uses molecular species as data storage elements, rather than the traditional circuits, magnetics etc. An illustrative example is the design of storage systems such as dynamic random access memory (DRAM). A basic DRAM consists of one capacitor and one transistor. The charge stored on the capacitor indicates the bit value (0 or 1). Thus a key design feature in the miniaturization of DRAM is the availability of capacitance as the feature size shrinks. Recent studies have shown that a DRAM capacitor with 0.14m feature dimensions has an effective capacitance of ~25 fF. If a DRAM unit is made on these dimensions a memory element density of the order 1 Gbit/cm2 can be achieved. DRAM based on molecular properties (feature size ~50nm) can have a memory density in excess of 1Tbit/cm2. Molecules that might be suitable for such purposes have recently been a subject of great interest. Porphyrin-based polymers are one of them. Porphyrins [1] are aromatic heterocyclic macrocycles composed of four modified pyrrole subunits interconnected at their -carbon atoms via methine bridges (=CH). Porphyrin-based polymers possess a very special characteristic of storing electric charge. Once a certain voltage is applied, the material oxidizes, releasing an electric charge. This is a reversible process, in effect creating an electric capacitor. This forms the basis of data storage with the information being stored in the oxidation state of the molecule. Section II of this paper discusses porphyrins, their information storing capability and superiority over other redox-active molecules. Section III discusses how this capability can be

Fig. 1. A porphin molecule, chemical formula C20H14N4, The chemical structure shown above, essentially consists of four pyrrole rings joined together by four methine (=CH-) groups to form a larger macrocycle ring.

heterocyclic. The compound itself is solid. Substituted porphines are called porphyrins. A. Synthesis Porphyrins occur naturally in crude oil, oil shale, coal or sedimentary rocks.

Fig. 2. The Rothemund synthesis, a condensation and oxidation process starting with pyrrole and an aldehyde to yield a porphyrin derivative.

The biosynthesis of porphyrins involves the formation of -

2 2012EE50545, Digital Electronic Circuits, I semester 2013-2014, IIT Delhi aminolevulinic acid (dALA) by the reaction of amino acid glycine with succinyl-CoA from the citric acid cycle. In laboratory porphyrins are synthesized using the Rothemund synthesis [2], [3]. Some green chemistry alternatives where the reaction is performed with microwave irradiation using reactants adsorbed on silica gel or at high temperature in the gaseous phase are also employed for synthesis. B. Information Storing Capability The information is to be stored in the oxidation state of the molecule. Porphyrins can provide three accessible oxidation states: the neutral state, monocation and dication. Since the oxidation states of the molecule can be changed at will (by applying suitable potential across the molecule), it is used as an information storage medium. C. Superiority over Other Redox-active Molecules Porphyrins are preferred over other redox-active molecules for a numerous reasons. Firstly, they can form stable radial cations and dications and undergo reversible electrochemistry, based on which, erasable electrical recording can be achieved. Secondly, since the information is stored in the different oxidation states and porphyrinic molecules exhibit three distinct states, multiple bits of information storage can be realized using these molecules, thereby providing a much higher storage density. Thirdly, the electrochemical potential of a porphyrin can be turned over a larger range (>0.5V) by the choice of central metal and peripheral substituents [4]. A. Storing Charge (Writing) Charge is stored (written) to the porphyrin SAM by the application of a voltage step (set at an oxidizing potential) which leads to a change in the oxidation states. This is a conventional experiment known as chronoamperometry. The potential of the step can be set so as to access one or more of the redox states of the porphyrin. The three redox states of the porphyrin can be employed to represent binary logic.

OXIDATION STATE

BINARY LOGIC

Neutral Monocation Dication

00 01 10

Fig. 4. The oxidation states of the porphyrin are assigned binary logic and thus data storage is made possible.

III. READING AND WRITING INFORMATION Direct electrical communication with the porphyrins is achieved by attaching the molecules to a surface with the use of a linker. Typically the molecules are attached to gold (Au) surface using thiol as a linker in a self-assembly process resulting in assemblies known as self-assembled monolayers (SAMs).

Current research has shown that SAMs of monomeric porphyrins retain charge for hundreds of seconds after disconnection of the applied potential, which is almost five orders of magnitude longer than the finest DRAMs available at present. The information stored on the SAMs is then refreshed (once the retention time is elapsed) similar to the practice performed while using DRAMs. B. Measuring Charge (Reading) The read operation can be thought as an inverse of the write operation. The charge stored on the porphyrin can be read using a counter electrode [5]. The counter electrode is connected to the SAM and current flowing through the electrode is measured. The current flowing through the electrode is directly proportional to the charge stored on the porphyrin. No current flows when the porphyrin is in neutral state (00), small current flows in monocationic state (01) and a large current flows when the porphyrin is in dicationic state (10). The measured current therefore tells about the information stored. C. Factors affecting Charge Retention The key to faster operations is charge retention. To save the cost of refreshing the memory frequently, longer charge retention times need to be achieved. The length and composition of the linker affects the rate of reading and writing as well as the duration of charge storage (i.e. charge retention time). The charge retention times can be enhanced by using longer linkers having greater electronic coupling with the Au surface to which the SAM is attached.

Fig. 3. A thiol-derived Zn porphyrin in a self-assembled monolayer (SAM).

3 2012EE50545, Digital Electronic Circuits, I semester 2013-2014, IIT Delhi the conjugated linker porphyrin SAMs are significantly smaller than those for PMn SAMs. This shows that the electronic properties of the linker have a strong influence on the charge retention durations, probably resulting from the greater electronic coupling of the PMn type between the surface and the porphyrin redox sites through the more conjugated linkers of the wire-linked molecules. The charge retention time thus is a function of many parameters including the inherent stability of stored charge and the barrier to electron transfer. Therefore the choice of molecules is very important feature in designing viable memory storage elements. IV. CONCLUSION The discussion on porphyrin SAMs indicates that they possess many characteristics which can be used to make them a medium to store information and thus function as molecularbased memory elements. These characteristics are summarized below. The charge retention in porphyrin-based SAMs is many order of magnitude larger than that in best semiconductorbased devices available at present. This property leads to lower power consumption and refresh rates, as well as greater memory density than is available using the semiconductor technology.

PORPHYRIN PEPM PEP EP PMn0 PMn1 PMn2 PMn3

T1/2/S 58 43 31 116 167 656 885

Fig. 5. Charge retention half-lives for thiol-derived Zn porphyrins in SAMs. Refer to Fig. 6 for structures of PEPM, PEP, EP and PMn. [6].

Fig. 6. Porphyrins for preparing SAMs with the designations EP (ethynylphenyl linker), PEP (phenylethynylphenyl linker), PEPM (phenylethylphenylmethyl linker) and PMn (phenylalkyl linker).

Fig. 7. Schematic representation of the architecture used for our molecularbased memory devices. A porphyrin layer is anchored to one of the two electrodes used in electrochemical cell designed to allow for the storage of digital information by varying the oxidation state of the porphyrinic ring. Each electrochemical cell is placed in a cross-array arrangement similar to those used in other microelectronic memory devices.

Molecular structures such as the porphyrin SAMs with It can be seen from figures 5 and 6 that the T1/2 values for

4 2012EE50545, Digital Electronic Circuits, I semester 2013-2014, IIT Delhi multiple oxidation states have the possibility of storing a large number of memory bits in a single memory cell. This type of multi-bit storage is not possible with semiconductor-based devices. Finally the molecular memory architecture just discussed can be schematically represented as below. But a major problem still remains. We still need to refresh the memory in a couple of seconds i.e. the memory, in a way, is still volatile. It would be tremendous if we are able to make the flash memory counterpart of molecular DRAMs. Further research is indeed being performed on non-volatile molecular memory which will not require frequent refresh thereby saving energy and lead to faster operations. With proper molecular engineering data retention for about 600 hours has been achieved. [7]
Monolayers, Journal of Vacuum Science and Technology B 18, 2359(2000). K.M. Roth et al., Comparison of Electron-Transfer and ChargeRetention Characteristics of Porphyrin-Containing Self-Assembled Monolayers Designed for Information Storage, Journal of Physics and Chemistry B 2002, 106, 8639-8648. Non-Volatile Molecular Memory, unpublished, available online: http://www.nasa.gov/centers/ames/research/technologyonepagers/nonvolatile_memory.html

[6]

[7]

Fig. 8. Data retention curve for non-volatile molecular memory-based technology.

This can also be employed in on-board data storage capabilities compatible with space explorations where limitations on mass, power and volume are immense. This field is quite promising and a lot needs to be done before we reach the limits of ultra-high density, low power consumption storage media. REFERENCES
[1] [2] [3] [4] [5] R.H Felton , The Porphyrins, edited by D. Dolphin (Academic, New York, 1978), Vol. V, pp. 53-126. P.Rothemund, Formation of Porphyrins from Pyrrole and Aldehydes, Journal of American Chemical Society 1937 57(10): 2010-2011. P.Rothemund, A New Porphyrin Synthesis. The Synthesis of Porphin, Journal of American Chemical Society 1936 58(4):625-627. Y.Song, D.Zhu, High Density Data Storage: Principle, Technology and Materials, World Scientific Publishing Company, 2009 K.M. Roth et al., Molecular Approach toward Information Storage based on the Redox Properties of Porphyrins in Self-assembled