![Page 1: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/1.jpg)
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
![Page 2: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/2.jpg)
PlanPlan
• Définition, quelques repères historiques
• Principes de base, structure et transport électroniquedans une jonction moléculaire
• Exemples de composants à l'échelle moléculaire
![Page 3: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/3.jpg)
Definition, introduction, Definition, introduction, foundations of the fieldfoundations of the field
![Page 4: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/4.jpg)
• “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
![Page 5: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/5.jpg)
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
![Page 6: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/6.jpg)
1rst evidence of tunnelingthrough a fatty acid LBmonolayer sandwichedbetween metal electrodes
Mann & Kuhn, JAP (1971)MPI
![Page 7: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/7.jpg)
Dimension
Courtesy of J.P. Bourgoin (LEM-CEA)
![Page 8: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/8.jpg)
Basic problems : electronic structure, Basic problems : electronic structure, basic devices and electronic transportbasic devices and electronic transport
![Page 9: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/9.jpg)
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
![Page 10: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/10.jpg)
Vondrak et al., J. Phys. Chem B (1999)
![Page 11: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/11.jpg)
single molecule single molecule →→→→→→→→ ensemble of moleculesensemble of molecules
![Page 12: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/12.jpg)
Charge transport, currentCharge transport, current --voltagevoltage
1µ2µ
Low bias:tunnel effect
1µ2µ
Higher bias:resonancethrough MO
gVe=− 21 µµ
low coupling
![Page 13: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/13.jpg)
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)
![Page 14: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/14.jpg)
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
![Page 15: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/15.jpg)
What can we do with molecules ? What can we do with molecules ? Which types of electronic devices?Which types of electronic devices?
![Page 16: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/16.jpg)
electronic function in moleculeselectronic function in molecules
S
SS
S
SS
CN
CNNC
NC16H33
semiconductor/metal
rectifyier
insulator
bistable, memory
switch
![Page 17: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/17.jpg)
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
![Page 18: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/18.jpg)
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
![Page 19: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/19.jpg)
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
![Page 20: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/20.jpg)
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
![Page 21: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/21.jpg)
capacitive molecular memorycapacitive molecular memory
+∆Q
∆I∆V∆…
![Page 22: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/22.jpg)
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)
![Page 23: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/23.jpg)
MMéémoiremoire molmol ééculaireculaire capacitivecapacitive
SiSiO2, 2 nm
C60, 1ML
Al2O3 (ALD), 30 nmSiO2 (PECVD), 26 nm
Hou et al., APL (2006)Cornell
![Page 24: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/24.jpg)
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 : ??
![Page 25: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/25.jpg)
resistive molecular memoryresistive molecular memory
Ron Roff
command
![Page 26: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/26.jpg)
S
S
SSHSH
Gplane > Gtwisté
G ~ G0 cos2θ
SSSHSH
S
![Page 27: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/27.jpg)
Vankataraman et al., Nature (2006)Columbia
![Page 28: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/28.jpg)
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
![Page 29: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/29.jpg)
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
![Page 30: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/30.jpg)
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
![Page 31: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/31.jpg)
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
![Page 32: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/32.jpg)
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)
![Page 33: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/33.jpg)
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)
![Page 34: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/34.jpg)
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.
![Page 35: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/35.jpg)
• 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
![Page 36: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/36.jpg)
![Page 37: Electronique mol éculaire : état de l'art & perspectives · Couplage electron-vibration moléculaire IETS fluctuations, bruit SiO 2 1nm Si highly doped SiO 2 1nm Si highly doped](https://reader034.vdocuments.us/reader034/viewer/2022050111/5f49065a19291f331509d976/html5/thumbnails/37.jpg)
Thank you!Thank you!