Molecular Switches

Lecture 17, 3/29/04

Readings for this Lecture:

Electronically Configurable Molecular-Based Logic Gates, by C. P. Collier, E.

W. Wong, M. Belohradsky etc.
Molecular Memories That Survive Silicon Device Processing and Real-World
Operation, by Zhiming Liu, A. Yasseri, J. Lindsey, etc.
Digital Logic Using Molecular Electronics, by Seth C. Goldstein and Dan
Rosewater.

Lecture Summary:
This Lecture presented a review on the research progress of using molecular-based
devices to build logic gates as well as memory elements. These devices exhibit potential
to be utilized as an alternative to CMOS circuits at nano-scale.

Philosophy behind Molecular Computing:

The technology of CMOS-based semiconductor industry has advanced at an amazing rate
over the past several decades. This phenomenon is widely cited as Moores Law, which
states the fact that transistor density on a silicon chip doubles every 18 months. However,
CMOS devices are reaching its fundamental physics limit nanometer scale and the cost
associated with constructing the facilities to manufacture these devices is prohibitively
high. Many researchers are exploring molecular alternatives to CMOS-based computing
paradigm. Chemically assembled electronic nano-computers (CAEN) are proposed as
alternatives to conventional circuitry and architecture and will be based on chemically
synthesized and assembled nano- or molecular-scale components.
With chemical synthesis and assembly, very small machines are able to contain vast
amounts of resources (devices composed of molecules). The basic operating and
programming principles of these machines would be the same as for present systems.
However, there are a few factors of chemical synthesis and assembly which distinguish it
from conventional lithographic technology. First, any chemically prepared system has to
be ordered (or crystalline) and currently it is impossible to build a system with arbitrary
complexity with chemical synthesis techniques. Maybe one day there will be
chromosome-based systems, which are able to grow into a complex system as human
being based on the gene information encoded in the chromosome. But at least this will
not become true in the near future. The system with ordered structure leads to an analogy
to cluster-based FPGA system and configurable computing is a suitable candidate for

chemically prepared systems. Second, in the process of chemical synthesis and assembly,
it is almost impossible to grow a perfect part with no defect components. This is due to
intrinsic finite chemical reaction yields, whereas any reliable computing machine requires
perfect complexity. As a result, any CAEN will have to tolerate an extremely large
number of defects. Defect and fault tolerance has to be incorporated into design of any
practical CAEN systems. The pioneering work of Teramac by HP lab has provided an
insight into the architectural direction of CAEN systems. Teramac manages to tolerate a
considerable amount of defect components by exploiting FAT-tree architecture.
In recent years, researchers have made impressive progress on the building block of logic
gates and memory elements with chemically prepared devices.

Molecule-Based Logic Gates:

Figure credit : Electrically Configurable Molecular-Based Logic Gates, by C. P. Collier etc

In order to implement the architectural idea of configurable computing, researchers have

developed an electronically configurable junction that consists of a molecular monolayer
and a tunneling barrier sandwiched between lithographical fabricated metal wires (Fig.1).
However, because switches are one-time configured, they cannot be used as random
access memory (RAM). But the advantage of molecular switches is that they can be
easily scaled to molecular scale without performance loss. Compared to CMOS-based
configurable devices (such as FPGA) when usually two wires are used to configure a
switch while the other two to read its state, molecular switches only require two wires to
achieve both functions. One voltage is used to read the switch while the other one with
opposite polarity is used for configuration. Normally configuration voltage is twice

Figure credit : Electrically Configurable Molecular-Based Logic Gates, by C. P. Collier etc

operation voltage and it provides enough margin to prevent molecular switches from
accidental reconfiguration.
Fig. 3 shows the voltage-current curve of molecular switches. Each switch is composed
of a monolayer of redox-active rotaxanes sandwiched between metal electrodes. There
are two states and the switches are irreversibly opened by applying an oxidzing voltage
across the device. The state of the switch is measured with monitoring current flow at
reducing voltage. In the closed state, the current is dominated by resonant tunneling
effect through the electronic states of the molecules. In the open state, the switch can
be seen as a resistor with extremely high resistance and the current flow is very small.
The data given are all measured in air at room temperature. For an open switch, the
measured current at 2V to 1.5V was much less (on the order of 15 to 30) than that of a
closed switch. The difference of high current level and low current level of these switches
is so large that they could be simplified as diodes in the design of logic gates. Fig. 4
shows a simple 2-input AND gate and a 2-/3-input OR gate based on molecular switches.
The implementation is in fact the same as diode-based wired-logic gates, with the

exception that they are electronically configurable and they are able to maintain a diodelike behavior over a wide voltage range.
In short, molecular switches have proved to be viable as building block of logic gates.
However, there are problems to be addressed. First, it is only one-time programmable and
thus cannot be used as reconfigurable logic. Second, there is static current for open
switches even though it is very small. The power dissipation due to static current has to
be studied. Third, molecular switches are inherently molecule-sized in only one
dimension, that is, the width of molecular layer. Fabrication technology has to be
developed to stack the switches in order to reduce area.

Figure 5. A schematic of a nanoBlock

Figure credit : Electrically Configurable Molecular-Based Logic Gates, by C. P. Collier etc

As far as system design with molecular devices is concerned, Goldstein and Rosewater
proposed a hybrid architecture which combines molecular self-assembly and
lithographically produced conventional CMOS structure. At nano or molecule scale, all
subprocesses are intrinsically self-directed and only at micron scale precise and reliable
lithographically generated circuitry is possible. Figure 6 shows a proposed nanoBlock
using molecular techniques. Basically MLA is a 2-D grid of reconfigurable molecular
diodes that can be configured into circuits based on diode/resistor threshold logic. Figure
2 is a nanoBlock that is configured into a 2-input AND gate. The reconfigurable nature
of this nanoBlock allows defect tolerance.
However, to build an operational circuit such as a sequential machine, both logic gates
and latches are required. A molecular latch is proposed for this purposed as shown in
figure 7 and 8. As it shows, the latch is load/drive ratio based and it requires pretty

complex clocking scheme to perform signal restoration as compared to CMOS-based

latches.

Figure 6. two-input AND gate implemented in a reconfigurable CAEN grid

Figure credit: Digital Logic Using Molecular Electronics

Figure 7. (a) Simple molecular latch circuit. (b) Load-line diagram (c) Simulation results showing latching
and voltage
Figure credit: Digital Logic Using Molecular Electronics

Figure 8. (a) The complete molecular latch and (b) the clocking methodology
Figure credit: Digital Logic Using Molecular Electronics

Unlike in CMOS technology where 3-terminal transistors are easily configured as latches
to hold and restore a signal, molecular switches/diodes are 2-terminal devices and it is not
trivial to construct a suitable latch structure while maintaining low complexity and low
static current.

Molecule-Based Memory:
In addition to logic gates built with molecular devices, researchers are also investigating
memory counterpart with molecular techniques. For molecular memories to compete with
conventional microelectronics, they must be compatible with semiconductors under
extreme conditions required for processing and operating a practical device. Whats
more, they do not degrade under large number of read-write cycles.
Liu and Yasseri etc discovered porphyrin-based molecules bound to Si(100) which
exhibit redox behavior useful for information storage as well as meeting the challenge to
compete with conventional microelectronics. The figure blow presents the molecular
structure of this specific porphyrin.

Figure credit: Molecular Memories That Survive Silicon Device Processing and Real-World Operation, by
Z. Liu, etc.

The high-temperature stability of porphyrins tethered to silicon surface is observed.

Different porphyrins structures are able to exhibit two/four accessible cationic states. The
figure below shows the voltammetric response of a porphyrins structure with two
accessible cationic states. The CV curve of porphyrins clearly exhibits its ability for
information storage and detectability.

Figure credit: Molecular Memories That Survive Silicon Device Processing and Real-World Operation, by
Z. Liu, etc.

However, in order to be utilized as a memory element, reversibility and long-term

stability is also required. Fortunately, porphyrins is able to fulfill both. For porphyrins
monolayer tethered onto silicon surface, two types of cycle can be performed and they
are (i) oxidizing the electrically neutral monolayer and (ii) reducing the resulting
positively charged monolayer to its electrically neutral state. The oxidation event is
equivalent to writing a bit of information while the reduction event is to erasing or
destructively reading out the information. The five CV curves in the following figure
shows the response of the system after 0, 2.5 x 104, 1.8 x 106, 1.1 x 10 9 and 1.0 x 1010
oxidation-reduction cycles. It is clear that the porphyrins is pretty stable for long period
of oxidative cycles. In addition, once an oxidation state is written into porphyrins, it is
able to retain the state for minutes and thus reduce refresh rate greatly. This is much
better than current DRAM cells.
In short, porphyrin molecules have exhibited great potential to be a strong candidate of
molecular memory. It tethers very well to silicon and the attachment is very robust over a
wide range of temperatures. It has very different CV curves based on its oxidation state.
Whats more, porphyrin is able to retain its oxidation state for minutes, which means long
refreshing cycle and low power consumption.

Figure credit: Molecular Memories That Survive Silicon Device Processing and Real-World Operation, by
Z. Liu, etc.

Conclusion:
The advent of physical limit of CMOS technology has triggered research for molecular
alternative for microelectronics industry at nano-scale. The research has been divided into
two main parts. One is the search for molecular building blocks for logic gates and
latches; the other is for molecular memories. Molecular switches are constructed to build
logic gates and porphyrin has proved to be stable molecule for molecular memories.
However, there are still too many issues (such as silicon compatibility and molecular
manipulation) to be addressed before mass production of molecular chips, which will
certainly motivate enormous follow-up researches.