eleleecctrontron--vvibibrarationtion ssccaatteritteringng ... · current (meir-wingreen) tthhee...
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ElectronElectron--vibration scatteringvibration scatteringin molecular transportin molecular transport
Alessandro Pecchia
CNR/CNISM - University of Roma “Tor Vergata”
CollaborationsCollaborations
EPSRC Symposium Warwick, August 24-28, 2009 2
http://flourish.org/upsidedownmap/
ElectronElectron--vibron scattering using NEGFvibron scattering using NEGF
EPSRC Symposium Warwick, August 24-28, 2009 3
ElectronElectron--vibron scattering using NEGFvibron scattering using NEGF
Quantum TransportQuantum Transport
1
0( ) [ ]r r r rL RG E E H
Electron propagator
eμL
μR
Device regionLeft contact
ee
Right contact
Electron in-scattering functions
EPSRC Symposium Warwick, August 24-28, 2009 4
( ) ( ) ( ) ( )r aG E G E E G E
2[ ]
L
R
eI Tr G G dE
h
L R
Kinetic equation for the electronic density
Current (Meir-Wingreen)
The DFTB approachThe DFTB approach
DFTB = DFT based Tight-Binding method
0
[ ] [ ] repk k k XC
k
E n n H n E n r E
0k
kH E S cKohn-Sham equation:
Density Functional:
EPSRC Symposium Warwick, August 24-28, 2009 5
k
[Porezag, et al Phys. Rev. B 51 (1995) 12947]
H [ ]V n n
onsite atomic energy levels
two-centre density superposition
SelfSelf--consitent extensionconsitent extension
0 ( )SccH H H nSelf consistent H:
(2)
,
( )1( ) ( ') '
' ( ')xcv r
E n r n r drdr q qr r r
Second order energy term:
EPSRC Symposium Warwick, August 24-28, 2009 6
[Frauenheim, et al. J. Phys.: Cond. Matt. 14 (2002) 3015]
1
2SccH S q
[Elstner, et al. Phys. Rev. B 58 (1998) 7260]
Correcting term in H obtained by variational theorem
electronelectron--phonon couplingsphonon couplings
= † †
,
ˆ ˆ ( )qq q
q
H H c c c c a a
The electron-phonon coupling Hamiltonian is derived by expanding to first orderthe TB-Hamiltonian with respect to the atomic positions.
H
EPSRC Symposium Warwick, August 24-28, 2009 7
02
,, ,
ˆq q
II q I I
Q
He
m Q
, , ,( ) ' ( ') ( ')
2q q
ph qq
iE dE G E E D E
Electron phonon self-energy, Born approximation:
IETSIETS –– molecular fingerprintsmolecular fingerprints
I
EPSRC Symposium Warwick, August 24-28, 2009 8
Elastic
InelasticV
h/e V
h/e V
h/e V
dI/d
Vd
2I/d
V2
h/e
Alkanethiols on AuAlkanethiols on Au
Reed’s experiment Calculations match and enhanceexperimental assignment
EPSRC Symposium Warwick, August 24-28, 2009 9
W. Wang, T. Lee, I. Kretzschmar & M.Reed Nano Lett. (2004) 4(4) 643-646
Solomon,Gagliardi, Pecchia, Frauenheim, Di Carlo, Reimers, Hush J.C.P. (2006) 124, 094704
Geometry dependenciesGeometry dependencies
higher energy
lower energy
EPSRC Symposium Warwick, August 24-28, 2009 10
Kusmerick et al. Nano Lett. (2004)
Selection/propensity rulesSelection/propensity rules
EPSRC Symposium Warwick, August 24-28, 2009 11
Selection/propensity rulesSelection/propensity rules
Conductance point groupConductance point group
Lost operators: axes C2x and C2y, inversion, Plane xy
• GM commutes with all molecular point-group symmetryoperators
• L and also R only commute with operators that do notinterchange the electrodes
• eg. Benzenedithiol (BDT): Full point group = D2h
Conductance point group = C2v
EPSRC Symposium Warwick, August 24-28, 2009 12
Lost operators: axes C2x and C2y, inversion, Plane xy
Solomon,Gagliardi, Pecchia, Frauenheim, Di Carlo, Reimers, Hush J.C.P. 125 (2006) 184702
BDT Buttiker channelsBDT Buttiker channels†)( MRML GGg Diagonalize
EPSRC Symposium Warwick, August 24-28, 2009 13
Black: total A1 + A2 + B1 + B2 red: highest gii blue: second highest gii
2 1
Junction orbitalsJunction orbitals
i j k l
Mil
Rkl
Mjk
Lij
MRML
GG *
†
)()Tr(
)(
g
GGg
diagonalize L,R => Junction-Conductance Orbitals
EPSRC Symposium Warwick, August 24-28, 2009 14
2
,
Tr( ) " | " | "L M Rii ij jj
i j
G gLeft-junctioninteraction
Right-junctioninteraction
Through-moleculeconnectivity
Junction ChannelsJunction Channels
EPSRC Symposium Warwick, August 24-28, 2009 15
Eigenvalue A1 A2 B1 B2
1 0.19 0.001 0.035 0.008
2 0.010 0.005 0.0004
3 0.0015 810-8 410-10
4 710-5 910-14
Solomon,Gagliardi, Pecchia, Frauenheim, Di Carlo, Reimers, Hush Nano Lett. 6 (2006)
Energy
Inelastic channelsInelastic channels
2( ) Tr
q
r r a ainc q L q R q
q eV
eI eV G G G G dE
h
2
,
| |L q Rq ii ij jj
i j
I A1
EPSRC Symposium Warwick, August 24-28, 2009 16
1 11 1A AA A
Propensity rule:
L,R are mainly A1
A1 (ag) modes are favouredB1
B1
B1
A1
A1
A1
A1
Diagonalize spectral matricesDiagonalize spectral matrices
2( ) Tr
q
a r r ainc q L q R q
q eV
eI eV G G G G dE
h
* 2( ) [( ) ] | |L R L q Rq q q ii ij jj
ij
strength Tr A A A A
Block-Diagonalize according to transportsymmetries
EPSRC Symposium Warwick, August 24-28, 2009 17
,L RA Diagonalize the A matrices and transformthe electron-phonon coupling matrices
Injectionchannel
Extractionchannel
Through-moleculeinelastic scattering
1 32 Totally symmetric =
symmetries
2( ) | |L q Rq ii ij jj
ij
strength A A
Simmetry and MOsSimmetry and MOs
EPSRC Symposium Warwick, August 24-28, 2009 18
Simmetry and MOsSimmetry and MOs
Eigenvalue A1 A2 B1 B2
1 3.44 0.011 27.4 2.26
2 0.144 0.071
3 0.128
EPSRC Symposium Warwick, August 24-28, 2009 19
Weighted Junction Cond. OrbitalsWeighted Junction Cond. Orbitals
Few dominant channels with rep.
A1 (a1g , b1u) and B1 (b3u ,b2g) :
2| |L q RI A A
B1
B1
B1
A1
A1
A1
A1
A1
EPSRC Symposium Warwick, August 24-28, 2009 20
1 1 1 1A BA B
11 11B BA A
2| |L q Rq ii ij jj
ij
I A AB1
Gagliardi, Solomon, Pecchia, Frauenheim, Di Carlo, Reimers, Hush, PRB 75, 174306 (2007)
Inelastic Interference patternsInelastic Interference patterns
EPSRC Symposium Warwick, August 24-28, 2009 21
Power DissipationPower Dissipation
EPSRC Symposium Warwick, August 24-28, 2009 22
Power DissipationPower Dissipation
Molecular heating&coolingMolecular heating&cooling
Thermal effects at the molecular scale represent an increasingly ‘hot’ topic
Theoretical and experimental challenges to measure nanoscale temperatures
EPSRC Symposium Warwick, August 24-28, 2009 23
Z. Huang et al. Nano Lett. 6, 1240 (2006)
N. Néel et al. PRL 98, 065502 (2007)
Z. Ioffe et al. Nature Nanotech., on-line doi:10.1038/nnano.2008.304
electronelectron--vibron scatteringvibron scattering
Elastic
V
μL
μ
R
Left contact
Device regionRight contact
Inelastich/e
1( ) [ ]r DFT r r rL R scattG E ES H
, , , , ,2 Im( )rL R L R L R L R L Rif if
( ) [ ]r aL R scattG E G G
EPSRC Symposium Warwick, August 24-28, 2009 24
Set up a steady-state solution for the vibronic populations
( ( )) 0q
q q q q A
dNR J N n T
dt
Rate equation:
Emission ratesEmission rates
2
[ ( ) ( ) ( ) ( )]q q qW E Tr E G E E G E dEh
q
q
q
WR
EPSRC Symposium Warwick, August 24-28, 2009 25
Delicate cancellation of terms which relays on current conservation
( 1)q q q q qR N E N A
0( )q q q
q
q q q
n T J EN
J A E
A. Pecchia et al., Phys. Rev. B 75, 035401 (2007)
( ( ))q q q q AR J N n T
SC phonon populationSC phonon population
- The calculation of Rq relays on a delicate cancellation of terms
- Current conservation is a necessary condition
- We use a predictor-corrector strategy and SCBA
SCBA LOOP
( ) ( ) ( 1) ( )q q q q q q q q qE N G E N G E
( ) ( ) ( ) ( )r aG E G E E G E
EPSRC Symposium Warwick, August 24-28, 2009 26
2
[ ( ) ( )]q q q qE Tr G E G E dEh
2
[ ( ) ( )]q q q qA Tr G E G E dEh
0( )q q q
q
q q q
n T J EN
J A E
( ) ( ) ( ) ( )G E G E E G E
SC POPULATION LOOP
CC6060 burning experimentburning experiment
Tip approaches at fixed V until C60 cracks.Molecules can be selectively burned
10-5
10-4
IC
rack
[A
]
-4,0 -3,5 -3,0 -2,5 -2,0 -1,5 -1,0 -0,5 0,0 0,5
10
100
1000
I[n
A]
Z [Å]
A
B
C
D
E
EPSRC Symposium Warwick, August 24-28, 2009 27
0,5 1,0 1,5 2,0 2,5 3,0
10-5
Bias [V]
G. Shulze et al., Phys. Rev. Lett. 100, 136801 (2008)
P = Icrack ∙Vcrack is not a constantbut shows features and plateaux
Dissipation ratesDissipation rates
The vibron lifetimes areproportional to the linewidths
The C60 is relaxed on the substrate
EPSRC Symposium Warwick, August 24-28, 2009 28
Vibron density of states.Shaded area Cu phonon DOS.
The vibron lifetime (Jq) are extractedadapting the Green’s functionsformalism to the molecule/substratecoupled dynamical system.
2
,
1Im ( )q q
q q
q
J e e
Heating and cooling processesHeating and cooling processes
μ
L
μ
R
μ
L
μ
R
μ
L
μ
R
μ
L
μ
R
Phonon emission (Eq) Phonon absorption 1 (Aq)
Phonon absorption 2 (Aq) Phonon dissipation (Jq)
EPSRC Symposium Warwick, August 24-28, 2009 29
e-h pair formation
( )q q q q molq q
U N n T
Definition of molecular temperature:
Model vs ExperimentsModel vs Experiments
Theory predictions Experiments
EPSRC Symposium Warwick, August 24-28, 2009 30
Tip-induced cooling
Power diss. in the moleculePower diss. in the molecule
Pmol P=IV
EPSRC Symposium Warwick, August 24-28, 2009 31
Pmol<<IV
Cooling effectsCooling effects
When the resonance approaches the bias windowseveral regimes take place subsequently:a) Resonant e-h absorption that cools the moleculeb) Intermediate regime with competing effects
a
b
c a b c
EPSRC Symposium Warwick, August 24-28, 2009 32
b) Intermediate regime with competing effectsc) Emission take over absorption
In the regimes a) and b) absorption wins over emission and themolecular temperature can decrease within a bias interval.
Temperature decreases <> Power dissipated increases
“Negative Differential Thermal Resistence” regime ?
Temperature vs biasTemperature vs bias
C60 on Si(100)C60 on Cu(110)
EPSRC Symposium Warwick, August 24-28, 2009 33
SummarySummary
Incoherent electron-vibron interactions:
- We can understand propensity rules in terms of coupling with L/Rprojected LDOS
- We can predict and analyze IETS
EPSRC Symposium Warwick, August 24-28, 2009 34
Disadvantages:
- Approximate method (requires testing)
- Repulsive potentials are needed for relaxations
- We can model and understand molecular heating
AcknowledgementsAcknowledgements
Prof. Aldo Di Carlo
Matthias Auf Der Maur, Post Doc
Fabio Sacconi, Post Doc
Alessio Gagliardi, Post Doc
Michail Povolotsky, Post Doc
Giuseppe Romano, PhD
Gabirele Penazzi, PhD
Marco Pacini, Student
Luca Salvucci, Student
Carlo Caringi, Student
EPSRC Symposium Warwick, August 24-28, 2009 35
Thank you
Carlo Caringi, Student
Prof. Jeff Reimers Univ. of Sidney
Gemma Solomon (PhD Sidney- Post Doc Chicago)
Molecular ChannelsMolecular Channels
i j k l
Mil
Rkl
Mjk
Lij
MRML
GG *
†
)()Tr(
)(
g
GGg
Diagonalize GM Molecular-Conductance Orbitals
EPSRC Symposium Warwick, August 24-28, 2009 36
i ij
Mjj
Rji
Mii
Lij
i
Mii
Rii
Lii GGG *2 )'('''|'|'')Tr(g
Current through eachmolecular-conductance
orbital
Interference betweenmolecular-conductance
orbitals
Solomon,Gagliardi, Pecchia, Frauenheim, Di Carlo, Reimers, Hush Nano Lett. 6 (2006)
Interference effectsInterference effects
EPSRC Symposium Warwick, August 24-28, 2009 37
i ij
Mjj
Rji
Mii
Lij
i
Mii
Rii
Lii GGGT *2 )'('''|'|'')Tr(g