Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration...
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Electronique Electronique mol mol é é culaire culaire : : é é tat tat de de l'art l'art & perspectives & perspectives D. Vuillaume Institute for Electronics, Microelectronics & Nanotechnology – CNRS, Lille “Molecular Nanostructures & Devices” group SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped Al SiO 2 1nm Si highly doped hydrogen carbon oxygen sulfur silicon Au Au -(CH 2 ) 3 -SH or C3-SH -(CH 2 ) 3 -CH 3 or C3 -(CH 2 ) 6 -CH=CH 2 or C8 1.0μm
Transcript of Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration...
Electronique Electronique molmol ééculaireculaire ::éétattat de de l'artl'art & perspectives& perspectives
D. VuillaumeInstitute for Electronics, Microelectronics
& Nanotechnology – CNRS, Lille“Molecular Nanostructures & Devices” group
SiO2 1nm Si highly doped
SiO2 1nm Si highly doped
Al
SiO2 1nm Si highly doped
hydrogen carbon oxygen
sulfur
silicon
Au Au
-(CH2)3-SH or C3-SH -(CH2)3-CH3 or C3 -(CH2)6-CH=CH2 or C8 1.0µm
PlanPlan
• Définition, quelques repères historiques
• Principes de base, structure et transport électroniquedans une jonction moléculaire
• Exemples de composants à l'échelle moléculaire
Definition, introduction, Definition, introduction, foundations of the fieldfoundations of the field
• “Information processing using photo-, electro-, iono-, magneto-, thermo-, mechanico or chemio-active effects at the scale of structurally and functionally organized molecular architectures”
(Adapted from: J.M. Lehn, Angew. Chem. Int. Ed., 1988, Noble Lecture)
Molecular Electronics - manipulate and control the position of one or few molecules- tailor their electronic properties to obtain useful devices
1 molécule - 1 monocouche
Pioneer resultsPioneer results
M1 A D M2
Fermienergy
LUMO
HOMO
LUMO
HOMO
Aviram-Ratner proposal
Aviram & Ratner, Chem Phys Lett (1974)IBM, New York U.
Theoretical suggestion of amolecular analog of the p-n junction:the donor-bridge-acceptor molecularjunction.
A - σ - D
1rst evidence of tunnelingthrough a fatty acid LBmonolayer sandwichedbetween metal electrodes
Mann & Kuhn, JAP (1971)MPI
Dimension
Courtesy of J.P. Bourgoin (LEM-CEA)
Basic problems : electronic structure, Basic problems : electronic structure, basic devices and electronic transportbasic devices and electronic transport
Molecule vs.Molecule vs.MetalMetal --MoleculeMolecule --Metal junctionMetal junction
« L'électronique moléculaire », J.P. Bourgoin, D. Vuillaume, M. Goffman & A. Filoramo.In "Les nanosciences, nanotechnologies et nanophysique", eds. M. Lahmani, C. Dupas P. Houdy (Belin, Paris, 2004), pp.400-449
∆
•hybridation•charge transfer
0
E
V
Vondrak et al., J. Phys. Chem B (1999)
single molecule single molecule →→→→→→→→ ensemble of moleculesensemble of molecules
Charge transport, currentCharge transport, current --voltagevoltage
1µ2µ
Low bias:tunnel effect
1µ2µ
Higher bias:resonancethrough MO
gVe=− 21 µµ
low coupling
V
I
V
I
C. Joachim et al. Phys. Rev. Lett. 74, 2102 (1995)Europhys. Lett. 30, 409 (1995)
D. Porath et al.J. Appl. Phys. 81, 2241 (1997)Phys. Rev. B 56, 9829 (1997)
control of the electrodecontrol of the electrode --molecule interface is molecule interface is crucialcrucial
Li et al., JACS (2006)Arizona U.
2.5x10-4G0
0.5x10-4G0
Patrone et al., Chem Phys (2002) LEM-CEA
What can we do with molecules ? What can we do with molecules ? Which types of electronic devices?Which types of electronic devices?
electronic function in moleculeselectronic function in molecules
S
SS
S
SS
CN
CNNC
NC16H33
semiconductor/metal
rectifyier
insulator
bistable, memory
switch
tunnel barriertunnel barrier
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
-1.0x10-14
0.0
1.0x10-14
2.0x10-14
3.0x10-14
4.0x10-14
5.0x10-14
6.0x10-14
7.0x10-14
Flux signal (V
)
Pho
tocu
rren
t (A
)
Photon energy (eV)
HTS DTS OTS
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
10-3
10-2
10-1
100
flux
D. Vuillaume et al., Phys. Rev. B (1998), Phys Rev. Lett. (1996)
A. Salomon et al., PRL (2005); Adv Mater (2007)
1.5 2.0 2.5 3.0
1x10-8
1x10-7
1x10-6
1x10-5
1x10-4
1x10-3
Monolayer thickness (nm)
Cur
rent
den
sity
(A
/cm
2 )
•E.E. Polymeropoulos et J. Sagiv, J. Chem. Phys. (1978)•C. Boulas et al., Phys. Rev. Lett. (1996)•J. Holmlin et al., J. Am. Chem. Soc. (2001)•D.J. Wold et al., J. Am. Chem. Soc. (2000,2001)•X.D. Cui et al., J. Phys. Chem. B (2002)
∆∆?
Au-S- : ~ 1.5 - 2.5 eVSi-C- : ~ 1.5 eV
Si-O- : ~ 4 - 4.5 eV
S. Lenfant et al. Phys. Stat. Sol. a (2006), IEMN-CNRSKushmerick et al. Nano Lett. (2004), NISTWang et al. Nano Lett? (2004), Yale
Couplage electron-vibration moléculaireIETS
fluctuations, bruit
SiO2 1nm Si highly doped
SiO2 1nm Si highly doped
Al
SiO2 1nm Si highly doped
hydrogen carbon oxygen
sulfur
silicon
Au Au
-(CH2)3-SH or C3-SH -(CH2)3-CH3 or C3 -(CH2)6-CH=CH2 or C8
localized (E,z) defects
N. Clement et al., PRL (soumis)IEMN-CNRS & Weizmann
molecular rectifying diodemolecular rectifying diode
D A
-2 -1 0 1 2
0
2x10-3
4x10-3
6x10-3
8x10-3
1x10-2
(a)LB3/5,chena/bo429d
Cur
rent
den
sity
(m
A/c
m2 )
Voltage (V)
CN
CNNC
NC16H33
Aviram & Ratner concept (1974)
A.S. Martin et al., Phys. Rev. Lett. (1993), Cranfield U.
R.M. Metzger et al., J. Am. Chem. Soc. (1997), Alabama U.
D. Vuillaume et al., Langmuir (1999), IEMN-CNRS
RR~30V>0
DA
simplified concept
-1.0 -0.5 0.0 0.5 1.0-2.5x10-5
-2.0x10-5
-1.5x10-5
-1.0x10-5
-5.0x10-6
0.0
5.0x10-6
1.0x10-5
OETS-thiophene HETS-phenyl HETS-thiophene
VT
Cur
rent
den
sity
(A
.cm
-2)
Voltage (V)S. Lenfant et al., Nano Letters (2003)D. Vuillaume, J. Nanosci. Nanotechnol. (2002)S. Lenfant et al., J. Phys. Chem. B (2006)IEMN-CNRS
Π
RR~37
capacitive molecular memorycapacitive molecular memory
+∆Q
∆I∆V∆…
U. California Riverside, North Carolina & ZettaCore Inc (2002) Liu et al., science (2003)
PorphyrinPorphyrin --based SAM on Sibased SAM on Si --H surfacesH surfaces
multi-redox = multi-valuedwrite ~ 10-3 - 10-5 srentention ~ 100-200 sr/w cycle : 1012
stable : 400°C (30min, inert atm)charge density ~16 µC/cm2
Kuhr et al., MRS Bul (2004)
MMéémoiremoire molmol ééculaireculaire capacitivecapacitive
SiSiO2, 2 nm
C60, 1ML
Al2O3 (ALD), 30 nmSiO2 (PECVD), 26 nm
Hou et al., APL (2006)Cornell
functionalized NW memoryfunctionalized NW memory
Duan et al., Nano Letters (2002) Harvard Univ
InP (10-30 nm) + Co phthalocyanine
on/off ~104
write ~ ?? srentention ~ 20min -600hr/w cycle : ??stable : ??
resistive molecular memoryresistive molecular memory
Ron Roff
command
S
S
SSHSH
Gplane > Gtwisté
G ~ G0 cos2θ
SSSHSH
S
Vankataraman et al., Nature (2006)Columbia
several attemptsseveral attempts ……
A. Szuchmacher Blum et al.,Nature Mater. (2005)NRL, Rice, Geo-Centers
Moore et al.JACS (2006)Penn State & Rice U.
Donhauser et al., Science (2001)Penn State & Rice U.
Au(111)/mica
avoid thiol on gold !avoid thiol on gold !
~8.3eV~800kJ/molSi-O
less sensitive to local structurecoupling through N lone pair
NH2/Au
~4.7eV~451kJ/molSi-C
~3.3eV~326kJ/molSi-Si
~1.8eV~180kJ/molAu-S
Very low energy
Loppacher et al., PRL (2003)U. Basel, IBM & CEMES-CNRS
~50zJ
θ=10°"OFF"
θ=55°"ON"
F. Moresco et al., Phys. Rev. Lett. (2001)U. Berlin & CEMES-CNRS
- CMOS FET : 0.1-1 fJ
- mol switch : 50 zJ
- kTLn2=2.8 zJ (@300K)
1012 "devices" at 1 GHz = 47 W
~ x104
~ x20
molecular transistormolecular transistor
McEuen & Ralph et al. Nature 2002Cornell
20-60 nm
Mottaghi et al. Adv Func Mater. (2007)ITODYS, IEMN-CNRS
Park et al, Nature 2002Harvard
Coulomb blokadeKondo effect
field effect
other molecular devicesother molecular devices
McEuen & Ralph et al. Nature 2002Park et al, Nature 2002
N. P. Guisinger et al, Nanoletters 4, 55 (2004)
Feringa et al., Adv. Mater. (2006)Univ. Groningen
NDR diodeMolecular transistor
Optical switch
Molecular spin-valve
Ralph et al., Phys Rev Lett (2004)
molecularmolecular --based circuitsbased circuits
J.M. Tour et al., IEEE Trans Nanotechnol. (2002)J.M. Tour et al., J. Am. Chem. Soc. (2003)
"NANOCELL"
A. Dehon et al., IEEE Trans Nanotechnol. (2003)
"Connecting nano to micro"
Crossnets Synaptic plaquette
Lykharev (2004)
NanoBlocks and NanoFabrics
Goldstein (2001)
Conclusions and perspectivesConclusions and perspectives
• Several functions and devices have been studied at the molecular scale : tunnel barrier, molecular wire, rectifying and NDR diodes, bistable devices and memories.– A better understanding and further improvements are
mandatory.– Need to be confirmed– What's about a true molecular 3-terminals device?
• Molecule-electrode coupling and conformation strongly modifies the molecular-scale device properties. Molecular engineering (changing ligand atoms for example) may be used to improve or adjust the electrode-molecule coupling.– A better control of the interface (energetics and atomic
conformation) is still compulsory.
• Towards molecular architecture and circuits: mainly the « cross-bar » architecture has been studied. Is it sufficient?– More new architectures must be explored (e.g. non Von
Neuman, neuronal…).– Molecular device interconnection?– 3D
Thank you!Thank you!
