Moletronics Presentation

Molecular Electronics (Moletronics)
Summer 2003
Y. Tzeng Auburn University
http://www.eng.yale.edu/reedlab/research/device/mol_devices.html#me mory http://www.trnmag.com/Stories/071801/HP_maps_molecular_memory_0718 01.html
http://www.nist.gov/speeches/SPIE_022601.pdf
MOLECULAR ELECTRONIC AMPLIFIER SMALLER THAN A DIME

CD 1967031 E&MP52.092
Electronics, January 22, 1960

The button-like object by the model with a pair of tweezers is actually an amplifier, which performs the same function as the conventional amplifier on the table. The tiny unit was developed and built by scientists of Westinghouse Electric Corporation in cooperation with the Air Force to demonstrate the feasibility of molecular electronics -- a new electrical engineering concept that could revolutionize the electronics industry and extend man's reach into space. A tiny amplifier just like th[is one] was incorporated into a phonograph system to replace a conventional audio amplifier. Westinghouse and Air Force officials report that molecular electronic units, or sub-systems, are more reliable and as much as 1000 times smaller than the most advanced electronics devices in use today. Original Caption by Science Service Westinghouse http://americanhistory.si.edu/scienceservice/052092.htm
Molecular Electronics
The US Air Force/Westinghouse project in 1959 came to nothing, because they couldnt work out how to achieve their goal. Researchers from Hewlett-Packard and the University of California, Los Angeles, announced in July 1999 that theyve actually made logic circuits that use molecular level chemical processes. These rely on organic molecules called rotaxanes that contain a ring of atoms threaded on a central molecule, like a bead on a wire, with blocking elements at each end to keep it on. Indeed, the new era of moletronics is beckoning just as silicon-era technologists are reaching their own stunning levels of transistor density. [New York Times, July 1999] The field of molecular electronicsmoletronicsis growing fast, and while researchers are keeping their feet on the ground for now, the ideas are flowing thick and fast. [Personal Computer World. Nov. 1999]
http://www.quinion.com/words/turnsofphrase/tp-mol1.htm
Molecular Amplifier
The graphical view illustrates the C60 amplifier: an electrical signal through STM tip, C60 molecule and copper surface (left) is amplified by about five times when the tip is lowered by the tenth of a nanometer, which requires only 10 mV (right)
*The scientific report "An electromechanical amplifier using a single molecule" was published in Chemical Physics Letters, Vol. 265, Nos. 3-5, page 353, February 7, 1997. http://www.zurich.ibm.com/news/97/n-19970307-01.html
DARPA Moletronics
Logic Devices -The design, synthesis, and testing of two interconnected molecular logic gates connected to the outside world, which produce a correct truth table. The devices must operate at room temperature, and the demonstrated configuration must be scaleable to densities of greater than 10 12 gates per square centimeter. Memory Devices -The design, synthesis, and testing of low-power, highspeed circuit architectures for high-density, terabit-level memories based on molecular electronic devices. The devices must have a functional 16-bit molecular memory connected to the outside world at a density of 10 15 bits per cubic centimeter. The molecular memory must be capable of performing a storage function at room temperature that is bistable and reversibly driven from one state to the other by an outside signal.
http://www.darpa.mil/MTO/mole/
Ultra-dense Molecular Electronic Computer Processor

(Defense Advanced Research Projects Agency Program 02/27/03)
The reliable, hierarchical assembly and fabrication of a prototype molecular electronic computer processor. Local molecular device densities of at least one hundred billion devices per square centimeter or fifty thousand nanodevices in a 100 square micron area. Clock rate of at least 10 kilohertz or equivalent. Consuming no more than 10 Watts per square centimeter of power. This nanoprocessor should be programmable and reprogrammable, and it should perform logic f unctionsincluding arithmetics. Logic and registers should be integrated and in communication with memory. The complexity of the original 1971-vintage microprocessors, i.e. the Intel 4004, but it would be 100,000 times smaller in area. Capable of being integrated with the molecular memory.
http://cbd.cos.com/cgi-bin/eps/spg/ODA/DARPA/CMO/BAA03-12/listing.html?notice=MOD
Ultra-dense Molecular Electronic Sensor System

(Defense Advanced Research Projects Agency Program 02/27/03) The reliable, hierarchical assembly and fabrication of a prototype molecular electronic sensor system. Operates in air or water. Have sensitivities and discrimination comparable to the animal kingdom, e.g. artificial dog?s nose. Consist of at least 1000 nanosensors per square micron (i.e., 100 billion per square centimeter). Consist of at least 1000 nanosensors per square micron (i.e., 100 billion per square centimeter). Unique identification of any of 255 different chemical or biological agents.
Ultra-dense Molecular Electronic Sensor System

Concentration as small as 500 parts per trillion. Allow for reuse of the sensor array up to at least 10 times. Integrated with the memory developed by the DARPA Moletronics Program. The interaction of a nanosensor with a chemical or biological agent must be transduced into an electrical signal. Chemical/biological interaction area or active detection area of the digital sensing system should range from 1 to 25 square microns. Defect-tolerant in their design and fabrication, as well as faulttolerant in their operation. Application of advanced nanofabrication and nanoassembly techniques. No more than one second of electrical response time after receptor attachment and no more than ten seconds of chemical response time after exposure of the sensor array to the environment. Modeling and simulation to ensure a complete, predictive understanding of device and system operation and performance.
http://cmliris.harvard.edu/html_natalya/research/device/device8.jpg
Carbon Nanotube Based Molecular/Nano Electronics
T. Rueckes, K. Kim, E. Joselevich, G.Y. Tseng, C.-L. Cheung, and C.M. Lieber "Carbon Nanotube-Based Nonvolatile Random Access Memory for Molecular Computing", Science 289, 94-97 (2000). http://cmliris.harvard.edu/html_natalya/research/device/device.html
Envisioned as arising from the interplay of the elastic energy, which produces a potential energy minimum at finite separation (when the upper nanotube is freely suspended), and the attractive van der Waals (vdW) energy, which creates a second energy minimum when the suspended SWNT is deflected into contact with the lower nanotube.
These two minima correspond to well-defined OFF and ON states, respectively; that is, the separated upper-to-lower nanotube junction resistance will be very high, while the contact junction resistance will be orders of magnitude lower.
http://cmliris.harvard.edu/html_natalya/research/device/device.html
IBM team made a " voltage inverter " Aug 26, 2001
Atomic Force Microscope image showing the design of an intra-molecular logic gate. A single carbon nanotube (shaded in blue) is positioned over gold electrodes to produce two p-type carbon nanotube field-effect transistors in series. The device is covered by an insulated layer (called PMMA) and a window is opened by ebeam lithography to expose part of the nanotube. Potassium is then evaporated through this window to convert the exposed p-type nanotube transistor into an n-type nanotube transistor, while the other nanotube transistor remains p-type.
Characteristics of the resulting intra-molecular voltage inverter. Open red circles are raw data for five different measurements on the same device (V=2V). The blue line is the average of these five measurements. The thin straight line corresponds to an output/input gain of one.
http://researchweb.watson.ibm.com/resources/news/20010827_logiccircuit.shtml
Dekker's group made their SET of one nanometer wide and 20 nanometers long. They used the tip of an atomic force microscope to put sharp bends in a single carbon nanotube. These bends served the same purpose as the barriers regulating the number of electrons passing through the carbon nanotube SET.
http://www.mtmi.vu.lt/pfk/funkc_dariniai/nanostructures/nanotubes.htm
IBM, 20020930
Researchers take a crystal of silicon carbide and heat it to about 1600 degrees centigrade in a vacuum. The heat causes the silicon to evaporate and the silicon's absence frees the carbon atoms to bond with other atoms. They bond to neighboring carbon atoms forming fragments of graphite which curl up to form nanotube seeds that grow with the addition of new carbon atoms. At the high temperature of the experiment it was found that the nanotubes become mobile and align themselves with the crystallographic structure of the substrate. Atonomic resolution STM image of a single carbon nanotube
http://www.research.ibm.com/resources/news/20020930_nanotube.shtml
http://nemo.physics.ncsu.edu/~nardelli/My%20Papers/science.pdf
Schematic of experiment. (left) A conducting AFM tip is used to measure the resistance of the NT-HOPG interface. (right) View of the interface from inside the tube. (B) The NT is in registry. Notice the ordered AB stacking of graphite lattices. In this geometry, the electronic wave function of allowed states in the NT (along tube axis) and the graphite (zigzag directions) are parallel. (C) The NT is out of registry. The NT Fermi-level States (dotted arrow) are no longer parallel to those in the graphite (solid arrow), and the momentum mismatch causes an increased interface resistance.
Resistance vs angle for MWCNT-HOPG contact
Buckyball-filled nanotube
The metallofullerenes (Gd@C82) and single-walled carbon nanotubes (SWNTs) were first formed. The nanotube was heated in dry air at 420 degrees Celsius to open both ends of the nanotube. The Gd@C82, once heated to a vapor, readily entered the opened tubes, and lined up inside the tubes at roughly 1 nanometer intervals.
Nanotube electronics
Semiconducting with bandgap ~20 meV to ~2eV Metallic capable of sustaining hundreds times electrical current than a metal
Can be a superconductor
Strong electro-mechanical coupling properties beyond electronics: Mechanically many times stronger than steel, but a few times lighter. Thermally more conductive than most crystals. Upon charge injection length changes much more than piezoelectrics does (not piezoelectricity).
Change between being chemically inert and selectively active.

Respond to light in conductivity as well as shape.
Jimmy Xu, Brown University, USA http://www.ee.sunysb.edu/~serge/ARW3/ABSTRACTS/Xu.pdf
Carbon nanotubes emit in the IR, 6 May 2003

The device does not rely on doping to create charge carriers, as silicon transistors do, but is 'biased' so that one part of the nanotube conducts electrons while the other conducts holes. This is achieved by the formation of Schottky barriers - potential barriers that electrons can tunnel through - at the source and drain. The electrons and holes recombined in the nanotube to emit infrared radiation at wavelengths longer than about 0.8 microns. This included light at a wavelength of 1.5 micrometres, which is widely used in fiber-optic communications The wavelength of the emission is determined by the band gap of the nanotube, which depends on the diameter of the nanotube.
http://optics.org/articles/news/9/5/5/1
http://www.cise.columbia.edu/NSEC/Downloads/NSECnanotech.pdf
Nanopore
Nanopore is a nanoscale metal / self-assembled monolayer / metal heterostructure. It provides well defined, stable and reproducible metallic contacts to a SAM within nanoscale area. Compared to STM and MCB, devices of this type are intrinsically stable and can be easily loaded into cryogenic systems and measurements at different temperatures can be easily carried out.
http://www.eng.yale.edu/reedlab/research/measure/mol_measure.html#nanopore
http://www.eng.yale.edu/posters150/pdf/reed4.pdf
The connections between three benzene rings, in which the orbitals overlapped (were conjugated) throughout, were made structurally weak, so that slight twists or kinks weakened or strengthened the conjugation of the orbitals. To the center benzene ring in the molecule, NO2 and NH2 groups were added, projecting outward from the string on opposite sides of the center ring. This asymmetrical configuration left the molecule with a strongly perturbed electron cloud. That asymmetric, perturbed cloud in turn made the molecule very susceptible to distortion by an electric field: applying an electric field to the molecule twisted it. Every time when a voltage is applied to the molecule, an electric field was set up that twisted the molecule and blocked current flow. With the voltage removed, the molecule sprang back to its original shape, and the current flowed again. This three-benzene-ring molecule acts like a voltage controlled switch.
http://www.mtmi.vu.lt/pfk/funkc_dariniai/nanostructures/molec_computer.htm
The methods used to produce molecular devices are the same as those of the pharmaceutical industry. Chemists start with a compound and then gradually transform it by adding prescribed reagents whose molecules are known to bond to others at specific sites.
The procedure may take many steps, but gradually the pieces come together to form a new potential molecular device with a desired orbital structure.
After the molecules are made, we use analytical technologies such as infrared spectroscopy, nuclear magnetic resonance and mass spectrometry to determine or confirm the structure of the molecules. The various technologies contribute different pieces of information about the molecule, including its molecular weight and the connection point or angle of a certain fragment. By combining the information, we determine the structure after each step as the new molecule is synthesized.
1. For the biphenyl molecule, it works as a rectifying diode: Byphenyl Molecule
Diode Behavior at Room Temperature

2. For the nitro-amine molecule, we observed strong NDR(negative differential resistance) behavior at low temperature:
Nitro-amine Molecule
http://www.eng.yale.edu/ree dlab/research/measure/mol_ measure.html#nanopore
Low Temperature NDR
3. The "nitro-only" molecule shows NDR at both low and room temperature: Nitro-only Molecule
http://www.eng.yale.edu/reedlab /research/measure/mol_measure .html#nanopore
Low Temperature NDR
Break Junction
A quantum point contact consisting of a few atoms can be realized with break junctions and pronounced conductance quantization is observed at room temperature. Molecules of benzene-1,4-dithiol are self-assembled onto the two facing gold electrodes of a conventional mechanically controllable break junction to form a statically stable gold-sulfur-aryl-sulfur-gold system, which allows for direct observation of charge transport through the molecules. Current-voltage I(V) measurements at room temperature demonstrate a highly reproducible apparent Coulomb blockade gap of ~0.7V. The conductance-voltage G(V) curves show two steps in both bias directions with the first step ~0.045 5S (22 M) and the second step ~0.075 5S (13.3 M).
The molecule does not conduct electrical current well at low applied voltages. When the applied voltage is increased to a specific level, the applied electric field twists the molecule and makes it become electrically conductive.
Diode
Cross section schematic of the Au-SAM-Ti-Au structure which is fabricated and probed using the nanopore process.
I-V plot of the 4thioacetatebiphenyl nanopore at 300k. The prominent rectifying behavior is due to the asymmetry
of the molecular heterostructure.

http://www.eng.yale.edu/reedlab/research/device/mol_devices.html#memory
The Switching Mechanism:
The conduction path in a conventional microelectronics transistor is turned on using an applied voltage at the gate electrode. Similarly, the conduction path thru a molecular switch is turned on by an applied voltage. The applied voltage is believed to cause a conformational shift which, in concert with the charging of the molecule, opens the conduction pathway. http://www.eng.yale.edu/reedlab/research/device/mol_devices.html#memory
Switches
Using the nanopore process and a 2'-amino-4,4'-di(ethynylphenyl)-5'-nitro-1benzenethiolate SAM low
temperature negative differential
resistance (NDR) and using a 4,4'-di(ethynylphenyl)-2'-nitro-1benzenethiolate SAM room temperature NDR have been
demonstrated. These devices work as two terminal switches: at
a specific applied voltage current will flow (device ON) at all other voltage values current does not flow (device OFF). Molecules:
2'-amino-4,4'-di(ethynylphenyl)-5'-nitro-1-benzenethiolate ("nitroamine" for short):
4,4'-di(ethynylphenyl)-2'-nitro-1-benzenethiolate ("nitro" for short):
The Device Characteristics:
I-V plot of nitro-amine nanopore at 60K. Shows very strong NDR with a peak to valley ratio of 1000:1 and a current density of 50 Amps/cm2.
I-V plot of nitro nanopore at 300K. Shows NDR with a peak to valley ratio of 1.5:1 and a current density of 16 Amps/cm2.
Series of room temperature I-V characteristics of a Au/biphenyldinitro SAM/Au device. The 1st sweep shows high conductivity On-state. The subsequent sweep shows low conductivity OFF-state. After a negative bias is applied, the high conductivity On-state is recovered.
Memory Cell
Using the nanopore process and a 4,4'-di(ethynylphenyl)-2'-nitro-1-benzenethiolate SAM a room temperature memory cell which can be configured as a RAM is demonstrated. These are two terminal devices that can be toggled between two conductivity states. The devices are written to the low conductivity state or "1" by applying a positive bias (+1.5V) and are erased to the high conductivity state or "0" by applying a negative bias (-1.5V). A device is read by applying a positive bias and measuring the resulting current.
The Molecules:
4,4'-di(ethynylphenyl)-2'-nitro-1-benzenethiolate (nitro for short):
Sequential I-V plot of nitro nanopore at 300K. The first trace shows the high conductivity state (blue, "0") and the second trace shows the low conductivity state (red, "1").
Molecular RAM:
The measured logic diagram of the molecular random access memory. The first input pulse configures the state of the cell, the second and third pulses read the cell and the fourth pulse resets the cell. These devices have been run continuously for many hours with no degradation in performance.
M. A. Reed, J. Chen, A. M. Rawlett, D. W. Price, and J. M. Tour, "Molecular random access memory cell", Appl. Phys.
Lett., 78, 3735 (2001). http://www.eng.yale.edu/reedlab/research/device/mol_devices.html#memory
Library of Molecules
Library of molecules that have been studied by the Yale University Group. Molecules of interest have various functional substitutes and end groups which affect molecular properties.
Schematic sketch of the formation of a conducting polymer nanojunction.

http://www.public.asu.edu/~ntao1/Publications/switch.pdf
Top: I-V characteristics of a Au-polyaniline-Au nanojunction. Bottom: Fluctuations near the onset of a switching from insulating to conducting states. The asymmetry of the fluctuation plateaus shown in the inset is due to the response of the Keithley 617 electrometer (slower than the STM preamplifier).
Charge transport current vs electrochemical potential for polyaniline nanojunctions with two Au nanoelectrodes separated with ~50 nm (a) and ~1 nm (b and c). The bias voltage between the nanoelectrodes in each case is 20 mV.
DARPA Moletronics Project
Directed Assembly of Molecular Logic Architectures using Functionalized Nanowires
http://jerg.ee.psu.edu/moletronics/index.htm
http://jerg.ee.psu.edu/moletronics/Introduction/
http://jerg.ee.psu.edu/moletronics/index.htm
Self-assembly is a phenomenon in which atoms, molecules or groups of molecules arrange themselves spontaneously into regular patterns and even relatively complex systems without intervention from outside.
HPs molecular memory
http://www.trnmag.com/Stories/071801/HP_maps_molecular_memory_071801.html
http://www.cise.columbia.edu/NSEC/Downloads/NSECnanotech.pdf
http://www.phantomsnet.com/nidconference5/abstracts/Abstract_Dekker.pdf
Molecular lithography builds up electronics

5 July 2002 Scientists from the Technion-Israel Institute of Technology have demonstrated a new molecular lithography technique for growing molecularscale electronic devices. The sequence-specific technique, which uses RecA protein, can deposit metal coatings at chosen
locations on strands of DNA.
There are basically four stages to the Technion team's lithography process. First, monomers of the protein RecA polymerize on a singlestranded DNA molecule to form a nucleoprotein filament. Then the nucleoprotein filament binds to an aldehydederivatized double-stranded DNA substrate molecule at a specific site where there is a homologous sequence. Treatment with a silver nitrate solution causes silver aggregates to form along the DNA substrate, everywhere apart from at sites protected by nucleoprotein filaments. Finally the silver aggregates act as catalysts for wet-chemical gold deposition, thus converting the unprotected regions of the substrate to conductive gold wires.
http://nanotechweb.org/articles/news/1/7/5/1
Toward the DNA Electronics, Tomoji KAWAI

ISIR-Sanken, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan DNA is one of the most promising molecules as the scaffold for molecular nanotechnology and nanoelectronics. DNA has the special double helix structure with -electron cores of well-stacking bases for the use of long-distance(e.g., 200) and one-dimensional charge transport. The investigations of DNA on the nanostructure, electrical conductivity and electronic states have significant implications for the application of DNA in electronic devices and in DNA-based electrochemical biosensors. It is worthily noted that divergent and controversial conclusions were reported in DNA-mediated charge transport. The direct measurements of the intrinsic electrical characteristics of polynucleotides using a conducting probe atomic force microscope have been performed using self-assembled DNA network. Poly[d(A-T)]2 and poly(dA)poly(dT) form the cross-interlaced mesh-like nanoscopic network and show the n-type rectification characters; Poly[d(G-C)]2 and poly(dG)poly(dC), on the other hand, construct the uniform two-dimensional reticulate structure and show the p-type rectified behaviors, presumably due to the different redox potentials of DNA bases. The conductivity of these molecules has been successfully controlled by chemical doping. It is found that the poly(dG)poly(dC) has the best conductivity and can act as a conducting nanowire. The conductive mechanism is discussed by the charge hopping model based on the SPM observation of DNA nanostructure. For the advanced construction of DNA based molecular memories and circuits, gold particles have been assembled in two-dimensional DNA networks. Gold particles are arranged artificially with
DNA molecular template as an average separation distance of 260nm. The pattern of

the complex is controlled by changing the concentration of the DNA solution, suggesting that this method is
effective in achieving the positional control of nano-scale molecular memories and circuits. T.Kawai et al; Appl.Phys.Lett.,77,3848(2000), Appl.Phys.Lett., 77,3105(2000),
Surf.Sci.Lett,432,L611(1999), J.Vac.Sci.Technol.B17,1313(1999), Jpn.J.Appl.Phys. 39, 581(2000), 38,L606(1999), 38,L1211(1999)
http://www.iis.u-tokyo.ac.jp/Labs/spm/Tokyo2001/abstracts/Kawai-T.html
Biopolymers such as DNA have been proposed to act as conducting

wires as well. We have carried out transport experiments on single short (30 base pairs) polyG-polyC DNA molecules between very closely spaced (10nm) metallic contacts. Nonlinear current-voltage curves indicate that DNA is a large-gap semiconductor that can be tuned to conduct carriers at very large bias voltages. At long length scales (100 nm) however, the transport currents through DNA are immeasurably small. I will show a number of experimental results from our lab and others. The prospects of using the intrinsic conductance properties of DNA for electronics are very very weak. However, DNA
does allow the construction of molecular-precise circuits by self assembly.

http://www.foresight.org/Conferences/MNT10/Abstracts/Dekker/
Picoscale/Nanoscale Science and Technology Vs Nanoscale/Microscale Science and Technology
http://ej.iop.org/links/27/Arl1t9UvJOw3Mxx247ijXg/na22r1.pdf
http://www.iop.org/EJ/S/UNREG/GjdY5f,DnzNFlA1BFYMkZQ/abstract/-featured=jnl/0957-4484/13/2/201
Thermodynamic Limit
Intramolecular Circuit
Time Circuit for Quantum Computing
Ready for the
Picotechnology?
More Molecular Diodes, Switches and Memory Cells

Utilizing A method for making electrical contact to both sides of a molecular SAM (Self-Assembled Monolayer): the nanopore molecules can be identified to be insulators, conductors, diodes, two-terminal switches and random access memory cells. A break junction method for making two terminal electrical contact to single molecule.
http://www.eng.yale.edu/reedlab/research/device/mol_devices.html

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Molecular Electronics (Moletronics)

Y. Tzeng Auburn University

http://www.eng.yale.edu/reedlab/research/device/mol_devices.html#me mory http://www.trnmag.com/Stories/071801/HP_maps_molecular_memory_0718 01.html

MOLECULAR ELECTRONIC AMPLIFIER SMALLER THAN A DIME

Electronics, January 22, 1960

Ultra-dense Molecular Electronic Computer Processor

Ultra-dense Molecular Electronic Sensor System

Ultra-dense Molecular Electronic Sensor System

Carbon Nanotube Based Molecular/Nano Electronics

Resistance vs angle for MWCNT-HOPG contact

Change between being chemically inert and selectively active.

Carbon nanotubes emit in the IR, 6 May 2003

1. For the biphenyl molecule, it works as a rectifying diode: Byphenyl Molecule

Diode Behavior at Room Temperature

http://www.eng.yale.edu/ree dlab/research/measure/mol_ measure.html#nanopore

Low Temperature NDR

http://www.eng.yale.edu/reedlab /research/measure/mol_measure .html#nanopore

Low Temperature NDR

of the molecular heterostructure.

The Switching Mechanism:

temperature negative differential

4,4'-di(ethynylphenyl)-2'-nitro-1-benzenethiolate ("nitro" for short):

The Device Characteristics:

Schematic sketch of the formation of a conducting polymer nanojunction.

DARPA Moletronics Project

Directed Assembly of Molecular Logic Architectures using Functionalized Nanowires

HPs molecular memory

Molecular lithography builds up electronics

locations on strands of DNA.

Toward the DNA Electronics, Tomoji KAWAI

DNA molecular template as an average separation distance of 260nm. The pattern of

Biopolymers such as DNA have been proposed to act as conducting

does allow the construction of molecular-precise circuits by self assembly.

Picoscale/Nanoscale Science and Technology Vs Nanoscale/Microscale Science and Technology

Time Circuit for Quantum Computing

Ready for the

More Molecular Diodes, Switches and Memory Cells

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