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2. Molecular Electronics. Molecular-scale electronics Molecular materials for electronics. Molecular wire Diode, rectifier Molecular switches Molecular memory Sensors Optics and optical switches Displays Electrochemical devices Molecular heterostructure and quantum well devices.

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2 molecular electronics
2. Molecular Electronics

  • Molecular-scale electronics

  • Molecular materials for electronics

  • Molecular wire

  • Diode, rectifier

  • Molecular switches

  • Molecular memory

  • Sensors

  • Optics and optical switches

  • Displays

  • Electrochemical devices

  • Molecular heterostructure and quantum well devices


Molecular electronic switching devices
Molecular Electronic Switching Devices

  • Electric-field controlled molecular switching devices including quantum-effect molecular electronic devices

  • Electromechanicalmolecular electronic devices

  • Photoactive/photochromic molecular switching devices

  • Electrochemical molecular devices

Bistability

Eb>kT


강의 순서

  • Information transfer

  • Interconnections

  • Electron transport

  • Molecular wire

  • Molecular rectifier

  • Molecular switches

  • Molecular RTD

  • Molecular memory

  • Atom relay


Computational limits
Computational Limits

  • Rolf Landauer

  • Nonreversible computer performing Boolean

  • logic operation requires minimum energy for a

  • bit operation,

P = nkBT ln2

Ex) energy required to add two 10 digit decimal numbers ?

P ~ 100kT ln2 ~ 3x10-18 joule per additions

1018 additions per joule

This is roughly the equivalent of 109 Pentiums !


Why molecular electronics
Why Molecular electronics ?

ENIAC, 1947

HP Jornada, 2000

17,468 vacuum tubes

60,000 pounds

16,200 cubic feets

174 kilowatts (233 horsepower)

  • Popular Mechanics (1949, March issue) predict that

  • someday ENIAC would contain only 1500 vacuum tubes

  • Now, Improve power efficiency by 108 and shrink by 108

  • Their prediction was based wrong foundation(vacuum-tube

  • technology)


Technology and biology
Technology and Biology

  • Technology Biology

  • Artificial Natural

  • Si-based C-based

  • Manufactured Self-assembled

  • Short history Long history

  • Function:logical Replication, adaptation…

  • numercal operation

  • Room temp Room temp


Microprocessor vs brain
Microprocessor vs Brain

  • MPU Brain

  • # of MOSFET ~ 107 # of cells ~ 1012

  • # of switches ~ 107 # of switches ~ 1011 neurons

  • # of connections ~107 # of connections ~ 1015 synapses

  • Wiring: fixed flexible

  • Architecture: serial parallel


Dram vs dna
DRAM vs DNA

DRAM DNA


Advantages of molecular electronics
Advantages of Molecular Electronics

  • Nano-scaled structures with identical size

  • Ultra High density: 106 times denser than Si logic circuits

  • Very cheap


Critical issues on molecular electronics
Critical issues on Molecular Electronics

  • What device types can provide bistable operation ?

  • How can these devices be organizedinto high

  • density 2D and 3D arrays ?

  • How can these devices be connectedin large number

  • to input/output lines?


Dynamic random access memory dram
Dynamic Random Access Memory (DRAM)

W1

W2

CMOS FET

D1 D2 (bit line)


Interconnection dilemma
Interconnection Dilemma

• Today’s chip densities are such that the wires

consume some 70% of the real estate

→ they cause some 70% of the defects that

lower chip yield

• The rate of defects in a chemically fabricated

nanocircuit : ppb level

→ million defects in a system containing 1015

components


Several fascinating possibilities
Several Fascinating Possibilities

• Defect-tolerant computing architecture: Heath, and Stoddart at UCLA, teamed up with Williams at HP

• Nanocell: Tour at Rice, Reed at Yale teamed up with Penn State

in Nov. 1999

• Switching with nanotubes: Lieber at Harvard University

• DNA assembly, computation: Seeman at New York University


Defect tolerant computing architecture
Defect-Tolerant Computing Architecture

  • Fat tree architecture enable one to route around and avoid the defect.

  • Manufacturing by chemical assembly is feasible.


Hpl teramac 1thz multi architecture computer
HPL Teramac1THz multi-architecture computer

  • Tera: 1012 operations per sec

  • Mac: Multiple architecture computer

  • 106 gates operating at 106 cycle/sec

  • Largest defect-tolerant computer

  • Contains 256 effective processors

  • Computes with look-up tables

  • 220,000 (3%) defective components


Nanotube interconnects
Nanotube Interconnects

  • Molecular scale wire with atomic perfection

  • Interconnect at high density

  • High thermal conductivity

  • Very stiff materials

Lieber et al


Wire conductance vs electron transfer
Wire conductance vs. Electron transfer

Molecular wire Intramolecular

electron transfer

Potential

Energy

Obsevablecurrent rate constant

Continuum electrode vibronic levels

Process electron tunneling electron tunneling

Theory I = (2pe/h)∫dE T2(E,V) k =(2p/h)T2DA(FC)

[fD(E)(1-fA(E+eV))

R(DA) P(D+A- )

Ef

Eg


Conductance landauer formula
Conductance : Landauer formula

m2

eVmol

eV

m1

m2

m1

I = (2e/h)∫dE T(E,V) [f(E-m1)-f(E- m2)]

  • F(E): Fermi function

  • T(E,V): transmission function

  • molecular energy levels and their coupling

  • to the metallic contacts

  • m1, m2 : electrochemical potentials

  • m1= Ef- eVmol

  • m2 =Ef+eV- eVmol

W. Tian et al, J. Chem. Phys. 109, 2874(1998)


Intramolecular electron transfer
Intramolecular Electron Transfer

D Bridge A

R(DA) P(D+A- )

Eg

RDA

k = (2p/h)V2DA(FC)

VDA = aexp(-bRDA), b= -(1/a)ln(2t/Eg)

VDA : electronic coupling through direct and

superexchange

FC: Frank-Condon factor

RDA : DA distance

a: length between electronic basis function in

the bridge structure

T: matrix elements between those bridge structure

Eg : energy gap

Chap1 and 2 in Molecular Electronics ed. J. Jortner and M. Ratner


Fabrication self assembled monolayer sam
Fabrication: Self-Assembled Monolayer (SAM)


Fabrication langmuir blodgett technique
Fabrication:Langmuir-Blodgett Technique

Setup for Langmuir-Blogett Deposition

Transferring Monolayers

&

Multilayer Film

P-Area Isotherms

http://www.public.iastate.edu/~miller/nmg/lbfilms.html


Conductance of molecular wire stm
Conductance of molecular wire: STM

  • Tip bias voltage = 1V,

  • Tunnling current = 10 pA

L. A. Bumm et al , Science 271, 1705 (1996).


Conductance of molecular wire mbj
Conductance of Molecular Wire: MBJ

  • Mechanically controllable break junction

  • Energy gap Gap: 0.7 eV

  • Conductance = 0.45 mS (R=22 MW)

MA REED,C Zhou, CJ Muller, TP Burgin, JM Tour, Science 278, 252 (1997)


Structural effects on conductance theory

Structural Effects on Conductance:Theory

  • Resistance increases exponentially with the # of the rings

  • Relative orientation of the rings

  • The bonding between them.

MP Samanta et al, Phys. Rev. B53, R7626 (1996)


Temperature effects theory
Temperature Effects : Theory

0

90

  • Unusual temperature induced large shift (~1eV) in is due to:

  • - The rotation property of the NO2 group

  • - Different symmetry of the states localized on the NO2 group

  • with respect to the orbitals of the carbon ring

M Di Ventra, SG Kim, ST Pantelides, ND Lang, PRL86, 288(2001)


Comparison of conductivity
Comparison of Conductivity

1,4 benzene polyphenylene carbon copper wire

ditiol wire (3ring) nanotube

App. Vol 1 1 1 2x10–3

(10cm)

Current (A) 2x10-8 3.2x10 -5 1x10 -7 1

Cross section

(nm2) ~0.05 ~0.05 ~3.1 ~3.1x1012

r=1nm r=1mm

Current density 2x1012 4x1012 2x1011 2x106

(e/sec-nm2)


Molecular rectifier

I

A. Aviram and M.A. Ratner,

Chem. Phys. Lett. 29, 277 (1974)

V

Molecular Rectifier

Forward

bias

electron donor

electron acceptor

p n

B

P

- +

- +

- +

+

-

TTF TCNQ

Tetrathiofulvalene

tetracyanoquinodimethane

πD*

πA*

EF

πD

πA


Energy levels of molecular orbitals
Energy Levels of Molecular Orbitals

DELUMO =ELUMO (D)- ELUMO (A)

Vacuum

f

Unoccupied

No bias

Off resonance

Ef

Occupied

Transmitted

electron

eVb

Forward bias

In resonance


Electrical rectification of lb films

R. M. Metzger et al, J. Am. Chem. Soc. 119, 10455 (1997)

Electrical Rectification of LB films


Energy levels
Energy levels

Electron

affinity

Ionization

potential

LUMO

HOMO

  • Ionization potetials ID for D end must be small and match as closely as

  • possible work function (f1) of metal layer (M1).

  • - If ID is too low, the molecule would oxidize in air

  • Electron affinity AA for A end must be as large as possible, match with

  • the work function metal layer M2(f2): this is not easy !


Molecular switches
Molecular Switches

  • Chemical switching

  • Electrochemical switching

  • Photochemical switching

V.Balzani et al, Acc. Chem. Res. 31, 405 (1998)


Molecular switches and gates rotaxane

4PF6-

O

O

O

O

O

O

O

O

O

O

O

O

O

O

O

O

+

+

N

N

N

N

N

N

+

+

CH2OH

Molecular Switches and Gates: Rotaxane

  • Closed at reducing voltage(-2V): current flow due to resonant tunneling

  • Open at oxidizing voltage(>0.7V): irreversible

C.P. collier et al, Science 285, 391(1999)


Electron transport in single molecule
Electron Transport in Single molecule

I

Ef

B1

B2

V

LUMO

I

Ef

Ef

V

M

M

HOMO

V

I

V=VLUMO

I

V=0 VOLT

V

DELUMO-HOMO

V=-VHOMO


Electron transport in single molecule1
Electron Transport in Single molecule

M  M*

M  M*

Ef

V

I

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

I

V

DELUMO-HOMO

Molecule switches

V = -VSWITCH

V = -VLOMO

Then, reset at the opposite bias

V = -VRESET


Configurable molecular and gate
Configurable Molecular AND Gate

4

+V

high

L

2

out

low

0

Current (10-9 Amps)

1

0

0

1

1

0

1

0

A=

B=

B

A

AND Gate Address Levels

A B C

0 0 0

1 0 0

0 1 0

1 1 1

A

B

A

B

C

C

R

V+

  • Difference between high

  • and low current levels:

  • 15 ~30

C.P. Collier, E.W. Wong et al.


Reversible molecular switches 2 catenane

Collier et al, Science, 289,1172 (2000)

Ti/Al : top electrode

LB monolayer

Reversible Molecular Switches: [2]Catenane

n-type ploy Si film:

bottom electrode

Si

SiO2

Ox.

Red.

Close

Open

  • Upon oxidation, the TTF become positively charged, the Coulombic repulsion between TTF+ and the tetracationic cyclophane causes to circumrotate.

  • Reversible switching :Opened >+2V, closed <-1.5V


Molecular field effect transistor r a reed and j m tour sci amer 282 86 2000

Molecular Field Effect TransistorR.A. Reed and J.M. Tour, Sci. Amer. 282,86 (2000)

Source Gate Drain


Reversible molecular switch with ndr effect
Reversible Molecular Switch with NDR Effect

  • Negative Differential Resistance ~ 400 MWcm2

  • Peak current denisty: 50A/cm2

  • Peak to valley ratio = 1030:1 (typical device=30:1)

  • Temperature induced shift : rotation of ligand(JACS,122,3015 (2001))

J Chen, MA Reed, AM Rawlett, JM Tour, Science 286, 1550 (1999)


Ndr effect continued
NDR Effect (continued)

Q=0 -1 -2

A

B

C

-

+

I

B

A

C

V

  • Anion conduction state

  • ON

  • Dianion insulatingstate

  • OFF


Molecular diode

Diodes

Using the nanopore process and a 4-thioacetatebiphenyl SAM we constructed a diode.

Molecular Diode

  • The prominent rectifying behavior is due to the asymmetry of

  • the molecular heterostructure.

  • The barrier from the bottom electrode is higher than the barrier for

  • electrons from the top T electrode

C. Zhou, M. R. Deshpande, M. A. Reed, L. Jones II, and J. M. Tour, Appl. Phys. Lett., 71, 611 (1997).


Lowest unoccupied molecular orbital lumo
Lowest Unoccupied Molecular Orbital (LUMO)

No LUMO states on the ring


Molecular ram
Molecular RAM

On

Off

  • 15min hold time DRAM at room temperature

  • Reversible molecular memory

  • Over one billion cycles and counting with no degradation

M.A. Reed et al, Appl. Phys. Lett. 78, 3735 (2001),

Z.J. Donahuer et al, Science 292, 2305 (2001)


Molecular resonant tunneling diode mrtd
Molecular Resonant Tunneling Diode (MRTD)

Unoccupied

Off

Occupied

1nm

On

  • Peak to valley ratio = 1.3 :1

  • Electrically active device by molecular orbital engineering

M.A.Reed, Proc. IEEE , Volume: 87, 652 (1999)


Synthesis of molecular devices
Synthesis of Molecular Devices

Source

Drain

Gate

  • Nano-scaled structures with identical size and shape

  • High density and low power

J.A Tour, Acc. Chem. Res. 33, 391 (2000)


Logic gate or
Logic Gate : OR

A B C

0 0 0

1 0 1

0 1 1

1 1 1

A

B

A

B

C

C

R

V-

CH2

Donor

Acceptor

wire

CH2

Donor

Acceptor

Long HC

Conjugated aromatic organic molecules


Electromechanical molecular electronics
Electromechanical Molecular Electronics

  • Single molecule electromechanical amplifier:

  • Joachim and Gimzewski Chem Phys. Lett. 265, 353 (1997)

  • - conductance modulation due to

  • electromechnical deformation of C60 cage

2. Atom relay transistor

Y. Wada, JVST A17, 1399 (1999)

  • Upon charging a gate, a mobile switching atom move into

  • a line of atomic wire


Inroganic organic hybrid circuits nanocell
Inroganic-Organic Hybrid Circuits: Nanocell

• Molecular wire having alligator clip

Metallic nanoparticles which are connected by functional molecules

1mm


Further challenges
Further challenges

  • Combining individual devices

  • Mechanisms of conductance

  • Nonlinear I/V behavior

  • Energy dissipation

  • Necessity of gain in molecular electronic circuits

  • Slow speed

  • New computer architecture

  • Synthesis of new molecules


숙제 1.

Read Feyman’s lecture “There is plenty of room at the bottom” listed at www.zyvex.com/nanotech/feynman.html

  • 공고

  • 금주 20일 (목요일): 휴강

  • 스케쥴 변경

  • week 7 : 10.16-10.18 Macromolecular nanostructures (김상율 교수)

  • week 8 : 10.20-26 중간고사

switch


CH712 물리화학특강 II 가을학기 강의 진도표

주제: Nano Science and Technology

ㅇ 강의담당: 김세훈, 유룡, 김상율, 김진백, 이윤섭, 이억균, 곽주현, 천진우

ㅇ 주관교수: 김세훈

ㅇ 연락처:전화: x2831; email:[email protected]

ㅇ 강의시간: 화,목 16:00-17:30

ㅇ 강의실: 자연과학동 2124호

ㅇ 참고문헌: Nanotechnology Research Directions: IWGN Workshop Report(1999)

http://itri.loyola.edu/nano/IWGN.Research.Directions/

ㅇ 강의내용: 기능성 나노구조의 합성, 제조, 물리 화학적 성질과 나노구조에 대한 특성분석

방법 등을 다루고 나노구조를 응용한 나노센서 및 나노소자의 개념을 소개함.

------------------------------------------------------------------------------------------

week 1 : 9. 4 Introduction (김세훈 교수)

week 1/2 : 9.6-9.11 Nano-characterization (김세훈 교수)

week 2/3 : 9.13-9.18 Nano dvice I (김세훈 교수)

week 3/4 : 9.20-9.25 Template based nanostructures (유룡 교수)

week 4/5 : 9.27-10.4 Template based nanostructures (유룡 교수)

week 6 : 10.9-10.11 Macromolecular nanostructures (김상율 교수)

week 7 : 10.16-10.18 휴강

week 8 : 10.20-26 Macromolecular nanostructures (김상율 교수)

week 9 : 10.30-11.1 Nano-fabrication and nano-lithography (김진백 교수)

week 10 : 11.6-11.8 Nano-quantum chemistry (이윤섭 교수)

week 11 : 11.13-11.15 Nano-thermodynamics (이억균 교수)

week 12 : 11.20-11.22 Nano-sensor and nano-device II (곽주현 교수)

week 13: 11.27-11.29 Nano-sensor and nano-device II (곽주현 교수)

week 14: 12.4-12.6 Nanoparticles and nanowires (천진우 교수)

week 15: 12.11-12.13 Nanoparticles and nanowires (천진우 교수)

week 16 : 12.15-12.21 기 말 고 사


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