Nanotechnology in the Year 2020

1
(No Transcript)
2
The Green Room 300K IBM STM
3
The Blue Room 4K LTSTM stability 0.0002 nm
4
LT 4K UHV STM at UCLA
5
Attoscience, ZeptoscienceTowards the
attojoule single molecule switch

• 10 nano n -9
• 10 pico p -12
• 10 femto f -15
• 10 atto a -18
• 10 zepto z 21
• 10 yocto y -24

6
Nanomechanics and tunneling in a single molecule
James K.Gimzewski Pico LabDepartment of
Chemistry and Biochemistry University of
California Los Angeles http//www.chem.ucla/Facult
y/gimzewski/ gim_at_chem.ucla.edu

7
Scanning Tunneling Microscopy

• The ultimate local probe microscopy
• The hands of NANO
• Uses quantum mechanical tunneling to feel atoms

8
The Art of moving atoms using a tip at low
temperatures
9
Diagnostics for Atomic Repositioning
Gimzewski In comparison atoms at low temperature
jump from site to site. They can be slide, be
pulled or pushed. They jump from site to site.
Molecules are more complex ..even a lead (Pb)
dimer does not jump with the lattice position.
Our molecules at room temperature ( previous
slide) tend to deform before they move.

• Rieder Group Berlin
• Berndt Group Aachen
• Joachim Group Tolouse

10
What is an STM image of a molecule?
Based on hexa-peri-hexabenzo-coronene (HBC)
A. Gourdon, H. Tang, C. Joachim, M. Pederson, R.
Schlittler and J.K. Gimzewski
11
Single Molecule Tunneling Barriers
Gimzewski In 1998 in a special commemorative
issue of the Proc of the IEE on 50 years of the
transistor we published this paper. We were the
only IBM paper in the issue ..dominated by Intel
etc. The idea is real simplewe use the fact that
squeezing a bucky ball by 0.1nm changes the
tunneling current flowing by a factor of 100. As
such it is a molecular amplifier with the
smallest active element ever. It has a gain of 5
( the same as the first transistor ). The speed
is limited by the vibration of the C60 to the
tera hertz regime.the wires and the tip limit it
to slow speed. Recent modeling by IBM France show
that with micromechnics we could get up to about
10 GHz and that it is not so dumb an idea. Again
it is an example of DEMONSTRATION driven research
to test the ultimate limits of nanofabrication.
It is not too important if we can put it in a
RISC processor in a few years .but with more
work molecules and nanomechanics may provide some
paradigm shifts The device operates on
MECHANICALLY MODULATED QUANTUM TUNNELING
Case 1 RESONANT TUNNELING Vt selected to match
molecular orbital energies Resonant tunneling via
HOMO or LUMO states Inelastic channels
opened Case 2 VIRTUAL RESONANT TUNNELING ( off
resonant ) Vt selected below LUMO and above HOMO
Molecular states broadened by substrate-molecule
interaction (Substrate wavefunction extends into
molecule)
http//www.zurich.ibm.com/News/Amplifier
C. Joachim J.K. Gimzewski Proc. IEEE 86(1998)
184
12
Counting with Molecules The Bucky Ball Abacus

• First demonstration of repositioning molecules as
  a counting device
• Counting from 0 to 10 using bucky balls
• Room temperature STM manipulation
• M.T. Cuberes, R.R. Schlittler J. K. Gimzewski,
  Applied Physics Letters, 69 (1996) 3016

13
Counting with Molecules The Bucky Ball Abacus
14
The Abacus in Art and Science Art 2 meters
high Science is 100 Million times smaller
15
Drexler Dreams Extensions of Macro-reality
Courtesy of NASA
16
Single Molecule Rotor Operating in a
Supramolecular Bearing One and a half of a
millionth of a mm in diameter
Only one atomic shift from FIXED
to FREE

• Jim Gimzewski et al IBM Research DivisionZürich
  Research Laboratories Science 281(1998) 531

17
A nanometer-sized gear would be ten thousand
times smaller than the microgear held by this
ant.

• The first nano-molecular rotor is observed

18
Nanomechanical DevicesSINGLE MOLECULE ROTOR
The Propeller
J.K. Gimzewski, C. Joachim, R.R. Schlittler, V.
Langlais, H. Tang and I. Johannsen  

• Hexa-t-butyl decacyclene
• One atom sized translation of molecule results
  in rotor
• Mass1.3x10-24kg
• Driven by Brownian rotational fluctuations

19
Molecular molecular rotor
J.K. Gimzewski, C. Joachim, R.R. Schlittler, V.
Langlais, H. Tang and I. Johannsen
20
STM Induced Rotation of O2 at 8K

• STM Induced Rotation of O2 at 8K.
• Molecule adsorbed on Pt(111)
• Rotation activated by voltage pulses
• Rotation rate varies with currentB.C.
  Stipe et al Science 279 (19998) 101

21
Maxwells demon and Feynmans ratchet and pawl
Brownian rotational fluctuations rectify using
the pawl chemically or by using tunneling?

• Cannot extract useful work out of background
  noise
• Second law of thermodynamics
• More recently kTln2 limit of computation
• Add colored noise to the system to effect energy
  conversion of thermal to unidirectional motion

22
Structure of di-t-butyl phenyl porphyrin
Bond angle of DTBP 90º
side
top
23
Cu-TBPP on Cu (100) Molecular cleavage induced
by STM
Gimzewski Molecular amputation the STM was used
to cut one of the legs of the molecule pointing
the way to building new molecules that may not be
synthesized by normal chemical routes. Its a
slow way to make molecules but it may allow
unique molecules that could self replicate (
maybe)

• Molecular recognition of four DTBP legs
• After exposure to several volts and high currents
  selective cleavage of legs evident
• Suggests that spacers and cleavage can be used to
  form reactive units for further molecular
  assembly

J. K. Gimzewski, T. A. Jung, M. T. Cuberes, and
R. R. Schlittler, Surf. Sci. 386, 101 (1997).
24
Molecular resolution and force spectroscopy of
Cu-TBPP porphyrin on Cu(100) AFM-STM

UHV STM Data
T. Jung, J.K. Gimzewski and R.R. Schlittler
25
Gimzewski Pushing around mlecules at room
temperature. In repositioning a total of 1000
atoms has been moved. This approach has the
advantage over atom by atom manipulation in that
the chemists could prefabricate bits and then the
STM does the final assembly. Compare building a
house from prefabricated walls etc. c.f using
single bricks.
Controlled Molecular Repositioning of Cu DTBP
porphyrin by STM at 300K

• ROOM TEMPERATURE OPERATION
• UHV on Cu(100)

• T. Jung, R.R. Schlittler, J.K. Gimzewski H. Tang,
  C. Joachim Science 271 (1996) 181

26
STM-ESQC-MM2 Calculations of STM Induced
Molecular Motion

• Science271(5246),181-184(1996).

27
Stick, Ball and Ball with Wobble Models of DTBP
Leg Rotation
28
Shape Shifting Molecules Cu-TBPP on metals
Gimzewski This is an example where STM was used
to determine in real space the conformation of
single molecules. The porphyrin changes its shape
in response to the type of metal and its
crystallography. These shape changes are
important in nature

• Conformational Adaptive Assembly
• Single Molecule Conformational Analysis
• A, B Cu (100)Aspect Ratio1Rotation90
  degrees
• C, D Ag (110)Aspect Ratio1.8Rotation30
  degrees

Jung, Schlittler and Gimzewski Nature386
,696-698(1997).
29
Molecular Conformation STM Cu-TBPP porphyrin on
Cu(100), Au(110) 2x1 and Ag(110)
Cu(100) STM/ nc AFM Au(110)1x2 Au (110)
annealed Ag(110)
90º
65º
45º
30º
30
Conformational Changes of Single Molecules
Induced by Scanning Tunneling Microscopy
ManipulationFrancesca
Moresco, Gerhard Meyer, Karl-Heinz Rieder, Hao
Tang, André Gourdon, and Christian Joachim
PHYSICAL REVIEW LETTERS 22 JANUARY 2001
31
Dynamic UHV nc-AFM

• Offers true atomic resolution
• Based on frequency shift of resonating cantilever
• Currently difficult to control experiment
• Operates well in UHV (high Q-factor)

32
AFM images of 9 molecules
Color is height f147 kHz A4.4 nm U
sample1.8 V (30 N/m) Frequency shift mean
shift -550 Hz Corrugation 1.2 Hz Damping
Energy A0 4.4 nm P 2.710-14W DP 9.010-16 W

Ch. Loppacher, M. Bammerlin, M. Guggisberg, E.
Meyer, H.J. Güntherodt, R. Lüthi, R. Schlittler,
J.K. Gimzewski (2001)
33
Sub-molecular resolution force spectroscopy

• High resolution nc-AFMpermits spatial definition
  of force spectra within a molecule
• Observe molecules before and after (verification)
• Lateral drift 5nm/hour
• Frequency shift recorded as function of proximity

34

• EXPERIMENTAL
• Df versus mean height
• Df (z) curves7 above Cu(100)2 above legs
• Dfchem (z) curve from subtraction of two data
  sets above
• fchem (z) curve

35
Determination of the short range tip-surface
forces

• k 30 N/m resonance frequency
• f 147 kHz
• decay length l 0.16 nm
• potential U0 0.02 atto-Joules.

36

• EXPERIMENTAL
• Df versus mean height
• Df (z) curves7 above Cu(100)2 above legs
• Dfchem (z) curve from subtraction of two data
  sets above
• Fchem (z) curve

37
Force (pN)
THEORY OF THE SINGLE MOLECULE ROTATION
Distance (Angstroms)
38
Force (pN)
EXPERIMENT THEORY OF THE SINGLE MOLECULE ROTATION
Force (pN)
Distance (Angstroms)
Distance (nm)
Min A 0.1 nN _at_ z1.4 nm Min B 0.2 nN _at_ z0.9
nm
39
Switching energy for a single C-C bond in Cu DTBPP

• Theory 88 zepto-joules
• Experiment 55 zepto-joules
• nmr data in solution for bond rotation
  (21kcal.mole-1)) 72 zepto joules for one
  molecule

40
Mechanical rotation of single C-C chemical bonds
in Cu DTBP porphyrin
MM2 with jellium description (100 nm diameter)
Atom-by-atom molecular description Cu(100) 2
layer 1.8 nm slab embedded in jellium 100
oriented tip 5 layer cluster supported by 100 nm
jellium sphere Site dependent response
of Deformation and forces Optimization at each
step in z
41
Full simulation
42
Switching energy 0.1 atto Joules

• 1 x 10-7 picojoules
• Lower than C60 molecular amplifier 1 attojoule
• For 10 12 molecular devices100W at 1 GHz

43
ENERGYDissipation
Nano-devices will approach the limits of Nature
governed by the 2nd Law of Thermodynamics Energy
Limit kT ln 2 At room
temperature 10-9 pJ kT ln2 zepto-joule
Molecular systems can enable such a limit to be
reached
We are here
44
Molecular Conformational Switch STM induced in
hexa-t-butyl decacyclene

• Morphing of action

45
MM2- STM ESQC Simulations of Switchingin
hexa-t-butyl decacyclene

• Captures essential features but not all

46
Acknowledgements

• R. Schlittler Ch. Loppacher, R. Lüthi
• M. Bammerlin, M. Guggisberg, O. Pfeiffer, E.
  Meyer
• H. Tang and C. Joachim
• Institute of Physics, University of Basel
• IBM Zurich Research Laboratory
• CEMES/CNRS,Toulouse

47
Raw data I-s and Frequency shift on approaching
leg
48
Bond Rotation in fee molecular state
49
Single Molecule Amplifier
Gimzewski In 1998 in a special commemorative
issue of the Proc of the IEE on 50 years of the
transistor we published this paper. We were the
only IBM paper in the issue ..dominated by Intel
etc. The idea is real simplewe use the fact that
squeezing a bucky ball by 0.1nm changes the
tunneling current flowing by a factor of 100. As
such it is a molecular amplifier with the
smallest active element ever. It has a gain of 5
( the same as the first transistor ). The speed
is limited by the vibration of the C60 to the
tera hertz regime.the wires and the tip limit it
to slow speed. Recent modeling by IBM France show
that with micromechnics we could get up to about
10 GHz and that it is not so dumb an idea. Again
it is an example of DEMONSTRATION driven research
to test the ultimate limits of nanofabrication.
It is not too important if we can put it in a
RISC processor in a few years .but with more
work molecules and nanomechanics may provide some
paradigm shifts The device operates on
MECHANICALLY MODULATED QUANTUM TUNNELING
MECHANICALLY MODIFIED VIRTUAL RESONANT
TUNNELING Mechanical deformation splits and
broadens HOMO-LUMO tails Example The Bucky Ball
Amplifier
C. Joachim J.K. Gimzewski
50
Single Molecule Electromechanical VRT Amplifier
Gimzewski In 1998 in a special commemorative
issue of the Proc of the IEE on 50 years of the
transistor we published this paper. We were the
only IBM paper in the issue ..dominated by Intel
etc. The idea is real simplewe use the fact that
squeezing a bucky ball by 0.1nm changes the
tunneling current flowing by a factor of 100. As
such it is a molecular amplifier with the
smallest active element ever. It has a gain of 5
( the same as the first transistor ). The speed
is limited by the vibration of the C60 to the
tera hertz regime.the wires and the tip limit it
to slow speed. Recent modeling by IBM France show
that with micromechnics we could get up to about
10 GHz and that it is not so dumb an idea. Again
it is an example of DEMONSTRATION driven research
to test the ultimate limits of nanofabrication.
It is not too important if we can put it in a
RISC processor in a few years .but with more
work molecules and nanomechanics may provide some
paradigm shifts The device operates on
MECHANICALLY MODULATED QUANTUM TUNNELING
MECHANICALLY MODIFIED VIRTUAL RESONANT
TUNNELING Mechanical deformation splits and
broadens HOMO-LUMO tails
C. Joachim J.K. Gimzewski Proc. IEEE 86(1998)
184
51
Self Assembly needs combined with function
Based on hexa-peri-hexabenzo-coronene (HBC)
A. Gourdon, H. Tang, C. Joachim, M. Pederson, R.
Schlittler and J.K. Gimzewski
52
Designer Molecules Lander I

• Symmetric four-lobed structures define contacts
• Self Assembly Chemistry
• Double Functionality

53
Conception of a Single Molecule Wire and contact
Designer Nanoscience SHAPE

• Design a Molecular Wire to assemble at a double
  atomic step
• Use spacers to electronically decouple wire from
  substrate
• Achieve a precisely defined contact in UHV
• Compute using STM-ESQC-MM2
• Probe metallic wavefunction leaking into wire
  using STM

V.J. Langlais, R.R. Schlittler, H. Tang, A.
Gourdon, C. Joachim, J.K. Gimzewski Phys. Rev.
Lett. 83(14), 2809-2812 (1999).
54
Designer Molecules USE SHAPE
Monolayer coverage

• Symmetric four-lobed structures
• Rectangular unit cell 1.62 nm X 2.43 nm
• Apparent internal corrugation 0.18 nm
• Image contrast is dominated by four legs
• Conformational adaptation evident
• From well defined 2-D structures
• Are highly mobile at 300K

STM image area 10 nm X 10 nm
55
15 X Self-docked Molecular Wires Intramolecular
tunneling barrier determination

• Approx. linear decay along molecular wireSlope
  ?z/?x 0.2
• Gm(Ef) G0 (Ef) e-?L
• jGm(x) exp (-F v1/2.z)
• ?(?z/?x). F v1/2
• F v4.1 eV
• F mol160 meV
• Theory 184 meV
• ? mol 4 nm-1

V t0.370 mV, I t70pA
h 0.36 nm
V.J. Langlais, R.R. Schlittler, H. Tang, A.
Gourdon, C. Joachim, J.K. Gimzewski Phys. Rev.
Lett. 83(14), 2809-2812 (1999).
56
Cross sectional Height profile along a single
Molecular Wire Intramolecular tunneling barrier
determination

• Approx. linear decay along molecular wireSlope
  ?z/?x 0.2
• Gm(Ef) G0 (Ef) e-?L
• jGm(x) exp (-F v1/2.z)
• GmG0 exp (- ? x)
• ?(?z/?x). F v1/2
• F v4.1 eV
• F mol160 meV
• ? mol 4nm-1
• Theory 184 meV

I-V at A and B I-s measurements here V t0.370
mV, I t70pA
57
TORANDS The Stator

• Torands are receptors for small molecules
• Central cavity is hollow
• Copper atoms can be trapped central cavity

Tom Bell (Nevada), R.R. Schlittler and J.K.
Gimzewski
58
Molecular Grippers

• National Research program Supramolecular
  Functional Materials
• Collaboration Prof. Diederich, ETH Zürich
• New mecano-receptor for C60
• Vases, Kites and Velcraplexes

59
Nanomolecular Grippers

• Chemo-mecano-grippers for specific molecules and
  self assembling structures
• Smart Functional Tips
• For Molecular Machine Assembly as self assembling
  bearings or stators

60
Nanomolecular Grippers with Francois Diederich
ETH Zurich

• Chemo-mecano-grippers for specific molecules and
  self assembling structures

STM of Optimized Self Assembled grippers on Au
61
The Brownian Molectronic Gate
Gimzewski How would you use a molecular wheel
as a part of a nano automobile or a nano watch
??? One way may to to use it to shuttle tunneling
electrons Here the rotor fluctuates and is
driven by a gate voltage to transport electrons
between Electrode 1 and 2 Just and idea. The
molecule could also be bi- or tri-stable forming
a mechanical memory element, ( this is the basis
of a Patent but you can talk about it)

• Supramolecular Bearing
• Asymmetric Tunneling Conductor
• Directed motion activated by gate voltage,
  current
• Directed motion activated by conformational
  changes
• Directed motion directed by inelastic
  tunnelingC evanescent waveguideD self
  assembling legsT Torand based cavity
• THREE MODES OF OPERATION-Rotational Barrier lt
  orgt than 10 kT ln 2 -RT or VRT

62
Hooks and Eyes Self Assembly of Nanotubes with
Fraser Stoddart

• Formation of nanotube snakes by the Hooks and
  Eyes approach where the recognition between
  crown ethers and dialkylammonium ions are used to
  reversibly thread the hooks and eyes.
• Adam Braunschweig

AFM SMFS for Optimized Self Assembly
63
Outlook

• Nanomechanics scales well with decreasing size in
  terms of signal to noise, energy dissipation,
  integration and eventually material use and cost
• Applications span medicine, IT to National
  Defense
• The shape, size, interactions, flexibility
  nano-architectures and suprainteractions in
  nanomechanical devices in NEMS, MEMS down to
  single molecules determine assembly and function.
  (Nanoarchitectonics)
• Every signal domain can be converted into a
  Nanomechanical response and extended general
  solutions realizable
• Need convergence of molecular and MEMS (NEMS) at
  .1-100nm

64
(No Transcript)
65

• k 30 N/m resonance frequency f 147 kHzdecay
  length l 0.16 nm and a potential U0 0.02 aJ.

66
Designer Molecules Lander I

• Symmetric four-lobed structures define contacts
• Self Assembly Chemistry
• Double Functionality

67
Designer Molecules USE SHAPE
Monolayer coverage

• Symmetric four-lobed structures
• Rectangular unit cell 1.62 nm X 2.43 nm
• Apparent internal corrugation 0.18 nm
• Image contrast is dominated by four legs
• Conformational adaptation evident
• From well defined 2-D structures
• Are highly mobile at 300K

STM image area 10 nm X 10 nm
68
15 X Self-docked Molecular Wires Intramolecular
tunneling barrier determination

• Approx. linear decay along molecular wireSlope
  ?z/?x 0.2
• Gm(Ef) G0 (Ef) e-?L
• jGm(x) exp (-F v1/2.z)
• ?(?z/?x). F v1/2
• F v4.1 eV
• F mol160 meV
• Theory 184 meV
• ? mol 4 nm-1

V t0.370 mV, I t70pA
h 0.36 nm
V.J. Langlais, R.R. Schlittler, H. Tang, A.
Gourdon, C. Joachim, J.K. Gimzewski Phys. Rev.
Lett. 83(14), 2809-2812 (1999).
69
Cross sectional Height profile along a single
Molecular Wire Intramolecular tunneling barrier
determination

• Approx. linear decay along molecular wireSlope
  ?z/?x 0.2
• Gm(Ef) G0 (Ef) e-?L
• jGm(x) exp (-F v1/2.z)
• GmG0 exp (- ? x)
• ?(?z/?x). F v1/2
• F v4.1 eV
• F mol160 meV
• ? mol 4nm-1
• Theory 184 meV

I-V at A and B I-s measurements here V t0.370
mV, I t70pA
70
Single Molecule Tunneling Barriers
Gimzewski In 1998 in a special commemorative
issue of the Proc of the IEE on 50 years of the
transistor we published this paper. We were the
only IBM paper in the issue ..dominated by Intel
etc. The idea is real simplewe use the fact that
squeezing a bucky ball by 0.1nm changes the
tunneling current flowing by a factor of 100. As
such it is a molecular amplifier with the
smallest active element ever. It has a gain of 5
( the same as the first transistor ). The speed
is limited by the vibration of the C60 to the
tera hertz regime.the wires and the tip limit it
to slow speed. Recent modeling by IBM France show
that with micromechnics we could get up to about
10 GHz and that it is not so dumb an idea. Again
it is an example of DEMONSTRATION driven research
to test the ultimate limits of nanofabrication.
It is not too important if we can put it in a
RISC processor in a few years .but with more
work molecules and nanomechanics may provide some
paradigm shifts The device operates on
MECHANICALLY MODULATED QUANTUM TUNNELING
Case 1 RESONANT TUNNELING Vt selected to match
molecular orbital energies Resonant tunneling via
HOMO or LUMO states Inelastic channels
opened Case 2 VIRTUAL RESONANT TUNNELING ( off
resonant ) Vt selected below LUMO and above HOMO
Molecular states broadened by substrate-molecule
interaction (Substrate wavefunction extends into
molecule)
C. Joachim J.K. Gimzewski Proc. IEEE 86(1998)
184
71
Nano-architectonics after NASI II

• Nanoarchitectonics The science of
  (nano)architecture, The art of constructing a
  system on the nano-scale all the way up to a
  common human (animal-internet) experience.
• Function and assembly through shape, form,
  fluctuations, dynamical changes, conformations,
  twisting, bending
• Suprainteractions the mortar that holds the
  bricks, the rubber bands and springs that holds
  the nano-parts in dynamical constructs.
• Machines through bond flexure, bending,
  conformation, folding, binding, lattice match,
  conformational adaptation, rotation, jumping
  sliding, Euler struts.
• HYBRID Mechanics, Chemical, Charges, Magnetic.

72
New Molecular System The Pancakes

• Disc-Type Polycyclic Aromatic Hydrocarbons(hexa-p
  eri-hexabenzo-coronene (HBC)
• 1958 Halleux et al
• Super-benzene
• Modification of substituents permits fine tuning
  of orbital energies
• Experiment originally designed for selective
  docking of Phenyl on monoatomic Cu(100) step

A. Gourdon, H. Tang, C. Joachim, M. Pederson, R.
Schlittler and J. Gimzewski
73
New Proposal Molecular Grippers

• National Research program Supramolecular
  Functional Materials
• Collaboration Prof. Diederich, ETH Zürich
• New mecano-receptor for C60
• Vases, Kites and Velcraplexes

74
Nanomolecular Grippers

• Chemo-mecano-grippers for specific molecules and
  self assembling structures
• Smart Functional Tips
• For Molecular Machine Assembly
• Swiss NSF Project in the Supramolecular
  Functional Materials NRP 47 (20Million SFr)

75
Nanomolecular Grippers with Francois Diederich
ETH Zurich

• Chemo-mecano-grippers for specific molecules and
  self assembling structures

STM of Self Assembled grippers on Au