Spin-dependent tunneling through organic molecules: spin...
Transcript of Spin-dependent tunneling through organic molecules: spin...
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Spin-dependent tunneling through organic molecules:spin scattering by organic radicals
P. LeClairPhysics & Astronomy, MINT, University of Alabama
G.J. Szulczewski, A. Gupta, S. StreetWeihao Xu
Chemistry, MINT, University of Alabama
Dina Genkina, Abel DemisseREU interns
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Organic Spintronics• Tunneling processes more crucial as length scales decrease
• Control with multiple degrees of freedom
• Spin transport & more general applications
• enable organic-based spintronics
• Organic materials are unique:- properties tailored through synthesis
• Fundamental understanding of transport- one molecular building block at a time- multiple degrees of freedom- interplay with optoelectronics?
• Create toolkit for device design
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Organic Spintronics• Tunneling processes more crucial as length scales decrease
• Control with multiple degrees of freedom
• Spin transport & more general applications
• enable organic-based spintronics
• Organic materials are unique:- properties tailored through synthesis
• Fundamental understanding of transport- one molecular building block at a time- multiple degrees of freedom- interplay with optoelectronics?
• Create toolkit for device design
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Organic semiconductors
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Organic semiconductors
Alq3
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Organic semiconductors
H2TPPAlq3
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Organic semiconductors
H2TPPAlq3
Pc
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Organic semiconductors
PTCDA
H2TPPAlq3
Pc
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Sample Preparation
SrTiO3
La0.67Sr0.33MnO3film (50-100 nm)
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Sample Preparation
SrTiO3
La0.67Sr0.33MnO3film (50-100 nm)
Pattern
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Sample Preparation
SrTiO3
La0.67Sr0.33MnO3film (50-100 nm)
Pattern Clean with~0.1% Br2
in ethanolfor 30 sec
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Sample Preparation
SrTiO3
La0.67Sr0.33MnO3film (50-100 nm)
Pattern
Vapor deposit organic
Clean with~0.1% Br2
in ethanolfor 30 sec
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Sample Preparation
SrTiO3
La0.67Sr0.33MnO3film (50-100 nm)
Pattern
Vapor deposit organic
Vapor deposit Co and Al through shadow mask
Clean with~0.1% Br2
in ethanolfor 30 sec
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Sample Preparation
SrTiO3
La0.67Sr0.33MnO3film (50-100 nm)
Pattern
Vapor deposit organic
Vapor deposit Co and Al through shadow mask
“Cross-bar” Area = 0.10 mm2
Clean with~0.1% Br2
in ethanolfor 30 sec
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Current-voltage and conductance curves
11 K LSMO
Co
15nm TPP
Xu et al. Appl. Phys. Lett. 90, 072506 (2007)
0.5 K
superconducting electrodesconfirms tunneling
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Normalized MR versus LSMO surface polarization
0
0.25
0.50
0.75
1.00
1.25
0 60 120 180 240 300
Norm
aliz
ed M
R
Temperature (K)
LSMO surface polarization (Park)Normalized MR for LSMO/TPP/Co
Park et al. PRL 81, 1953 (1998)
no apparent spin loss through TPP
T dependence just LSMO
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
• thin film SC in H (~2-3T) Zeeman split quasiparticle DOSmeasure dI/dV ~ NscNfm
• nonmagnetic : symmetric -- equal # of spins
• magnetic: asymmetry = spin polarization
robust, microscopic theory
“directly” gives spin imbalance of tunneling current
Meservey-Tedrow tunnelingbarrier
FM
SC
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
T= 0.36 KH= 3 TH= 0 TT = 500mKP ~ 37%H = 0H = 3T
Al / AlOx / TPP / Copolarization is not decreased by TPP
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
increased conductance at low bias, low T ...
evidence of magnetic excitations!
dI/dV
Vmagnon scattering
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Magnetoresistance of Co/20 nm TPP/LSMO
Xu et al. Appl. Phys. Lett. 90, 072506 (2007)
sizable MR observed
up to 40% at 10K
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
so what’s the problem?
• still to complicated• need a simpler starting point for structure-
property correlation
• so we go ‘back to the future’ … (again)
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Molecular Tunnel Junctions• One layer of a simple, flexible molecule - benzoic acid derivatives• Model system for more complex molecules - ‘scaffolding’• Correlate transport and molecular structure
organic
pinned FM
free FM
Al2O3
TransportConductance (V,H,T)
Spin-polarized tunneling
StructurePhotoemission (UPS,XPS)
Raman/IRInelastic electron tunneling
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Molecular Tunnel Junctions• One layer of a simple, flexible molecule - benzoic acid derivatives• Model system for more complex molecules - ‘scaffolding’• Correlate transport and molecular structure
organic
pinned FM
free FM
Al2O3
TransportConductance (V,H,T)
Spin-polarized tunneling
StructurePhotoemission (UPS,XPS)
Raman/IRInelastic electron tunneling
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Molecular Tunnel Junctions• One layer of a simple, flexible molecule - benzoic acid derivatives• Model system for more complex molecules - ‘scaffolding’• Correlate transport and molecular structure
organic
pinned FM
free FM
Al2O3
TransportConductance (V,H,T)
Spin-polarized tunneling
StructurePhotoemission (UPS,XPS)
Raman/IRInelastic electron tunneling
Self-assembly yields well-ordered monolayers
AlAl2O3
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Sample Preparation
Al (~10 nm)shadow mask
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Sample Preparation
Al (~10 nm)shadow mask
deposit benzoic acid from solution
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Sample Preparation
Al (~10 nm)shadow mask
deposit benzoic acid from solution
Vapor deposit Co or Pb through shadow mask
Center for Materials for Information Technologyan NSF Materials Science and Engineering Center
Sample Preparation
Al (~10 nm)shadow mask
deposit benzoic acid from solution
Vapor deposit Co or Pb through shadow mask “Cross-bar”
Area = 0.10 mm2
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
IETS: is there transport through the molecule?• tunneling electrons excite vibrational modes
– see Raman & IR modes– no strong selection rules
• when eV ≥ hv– stepped increase in dI/dV– new set of final states available– unambiguous - transport through molecule
• example: studying model catalysts– CO on Rh/Al2O3 -- CO vibrations
“tunneling energy loss spectroscopy”
detail: – tiny signals … challenging
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
IETS: is there transport through the molecule?• tunneling electrons excite vibrational modes
– see Raman & IR modes– no strong selection rules
• when eV ≥ hv– stepped increase in dI/dV– new set of final states available– unambiguous - transport through molecule
• example: studying model catalysts– CO on Rh/Al2O3 -- CO vibrations
“tunneling energy loss spectroscopy”
detail: – tiny signals … challenging
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
IETS: is there transport through the molecule?• tunneling electrons excite vibrational modes
– see Raman & IR modes– no strong selection rules
• when eV ≥ hv– stepped increase in dI/dV– new set of final states available– unambiguous - transport through molecule
• example: studying model catalysts– CO on Rh/Al2O3 -- CO vibrations
“tunneling energy loss spectroscopy”
detail: – tiny signals … challenging
d2I/dV2
dI/dV
Vhv
Vhv
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
IETS: is there transport through the molecule?• tunneling electrons excite vibrational modes
– see Raman & IR modes– no strong selection rules
• when eV ≥ hv– stepped increase in dI/dV– new set of final states available– unambiguous - transport through molecule
• example: studying model catalysts– CO on Rh/Al2O3 -- CO vibrations
“tunneling energy loss spectroscopy”
detail: – tiny signals … challenging
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
IETS: is there transport through the molecule?• tunneling electrons excite vibrational modes
– see Raman & IR modes– no strong selection rules
• when eV ≥ hv– stepped increase in dI/dV– new set of final states available– unambiguous - transport through molecule
• example: studying model catalysts– CO on Rh/Al2O3 -- CO vibrations
“tunneling energy loss spectroscopy”
detail: – tiny signals … challenging
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
How to measure a derivative?
• drive system with Vdc + δVacsin ωt• measure response at ω
frequency / phase sensitive technique
… lock-in amplifiers (talk to Dr. Enders)
€
I(Vdc + δVac cosωt) = I(Vdc ) +dIdV
δVac cosωt( ) +d2IdV 2
δIac2
4cos 2ωt( )
+K
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
(1) original nice idea ...
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
(1) original nice idea ...
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
(1) original nice idea ...
DC switch20k40k400k1M
AC switch1k10k100k1M10M
pin board connector
1 ac input from SW
2 dc input from SW
3 BNC ground
4 -V
5 +V
6-10 NC
11 com/BNC ground
12 to pin 4 LH0063K
13to pin 3 LH0063K
feedback
U1-U3-U4-U5 = OP07U2 = LF351U6 = LH0063K
(2) the “Danny filter” ...
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
(1) original nice idea ...
DC switch20k40k400k1M
AC switch1k10k100k1M10M
pin board connector
1 ac input from SW
2 dc input from SW
3 BNC ground
4 -V
5 +V
6-10 NC
11 com/BNC ground
12 to pin 4 LH0063K
13to pin 3 LH0063K
feedback
U1-U3-U4-U5 = OP07U2 = LF351U6 = LH0063K
(2) the “Danny filter” ...
(3) implementation ...
dI/dV: lock in to fd2I/dV2 (IETS): lock in to 2f
‘constant resolution’ modesoftware feedback to maintain
modulation
Rthing
Rprecise
DC
LIA
I & dI
V & dV+D
C
LIA
Vdc
Vac
Σ
IETS setup
THE UNIVERSITY OF ALABAMA CENTER FOR MATERIALS FOR INFORMATION TECHNOLOGYAn NSF Science and Engineering Center
Quantum Design PPMS R(T,H) T: 350mK -- 400K 3He fridge H: 0 -- 7T scriptable …
+
Home-built electronics dI/dV(V,T) d2I/dV2(V,T)
Transport facilities
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center IETS: we really have transport through the molecule
T = 2K
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center IETS: we really have transport through the molecule
T = 2K
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
JASCO FT/IR-4100_ATRScan #: 128Resolution: 2 cm-1
ATR crystal
IR beamTo detector
Sample
1 umEvanescent wave
ATR-FTIRwhat is the state of the molecule?is it still there?
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
ν: stretch; β: in-plane bend; γ: out-of-plane bend.
COO- symmetric modes - monodentate
T = 2K
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
AlAl2O3
AlAl2O3
Co Co
I III
I 3d
N 1s Al/Al2O3/BA/(Co or Pb)
Co reacts with heavier halogens
Pb does not
halogen substitution leads to organic radicals
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Conductance Through Benzoic Acids• Vary para- substituent
• Controlled introduction of radicals
AlAl2O3
AlAl2O3
Co Co
I III
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
size of zero-bias anomaly scales with degree of reactiononly very tiny effects for fluorobenzoic acid (or cyano)slightly larger for chlorobenzoic acidhuge for iodobenzoic acid
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
when we have a reaction …
… there is an unpaired electron
… which means an unpaired spin
… which gives a Kondo resonance(TK~20K)
(wacky quantum interference)
(many body effect)
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
H=0
H=7T
in a field, Kondo peak suppressed small “well” carved out of it ...
Al/Al2O3/ 4-iodobenzoic acid / Co T = 2K
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Spin-dependent Scattering by Organic Radicals• Organic radicals = unpaired electron• Should have ‘normal’ spin flip scattering• Revealed through application of H
fit gives g~2 … consistent
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
More details: • fit to high field data gives g ~ 2 … expected• signature logarithmic (V,T) dependence of Kondo peak in H=0• Kondo, H-dependent part are small terms
V-independent parts much largerspin scattering dominates conductance
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Building a Molecular Spin Transport Toolkit
• Porphyrin derivatives (E. Galoppini, Rutgers)
- control orientation- Dr. Choe ...
• Phthalocyanine derivatives -CoPc, F16CuPc-tune spin-orbit scattering via TM ion
• Lanthanide complexes- RE3+ controls spin dynamics- strong exchange
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
• new families of (known) moleculesspin transport is unknown
• build knowledge block by block
• systematic variation
• new tools and synergy transport ↔ structure
• designer toolkit for spin transport
• Spin-dependent scattering dominates with radicals- General mechanism!
Building a Molecular Spin Transport Toolkit
thanks to: NSF MRSEC grant No. DMR 0213985.
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Organic Spintronics• Understand spin injection & transport• Enable organic-based spintronics
• Organic materials are unique:- properties tailored through synthesis
• Fundamental understanding of transport- one molecular building block at a time- multiple degrees of freedom- interplay with optoelectronics?
• Create toolkit for device design
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Organic Spintronics• Understand spin injection & transport• Enable organic-based spintronics
• Organic materials are unique:- properties tailored through synthesis
• Fundamental understanding of transport- one molecular building block at a time- multiple degrees of freedom- interplay with optoelectronics?
• Create toolkit for device design
organicpinned FM
free FM
Two terminal: OLED, MTJ, spin valve
The University of Alabama Center for Materials for Information TechnologyA NSF Materials Research Science and Engineering Center
Organic Spintronics• Understand spin injection & transport• Enable organic-based spintronics
• Organic materials are unique:- properties tailored through synthesis
• Fundamental understanding of transport- one molecular building block at a time- multiple degrees of freedom- interplay with optoelectronics?
• Create toolkit for device design
organicpinned FM
free FM
Two terminal: OLED, MTJ, spin valveThree terminal: FET, logic, memory
organic Al2O3
FM FM
gate