Molecular Spintronics

Gabriel Aeppli Andrew Fisher Nicholas Harrison Sandrine Heutz 4, Chris Kay 5 and Des McMorrow 1 Tim Jones
1

1,

1,

2,

3,

Department of Physics and Astronomy, London Centre for Nanotechnology, University College London, London WC1E 6BT, U.K. 2 Department of Chemistry, London Centre for Nanotechnology, Imperial College London, London SW7 2AZ, U.K. 3 Department of Materials, London Centre for Nanotechnology, Imperial College London, London SW7 2AZ, U.K. 4 Department of Chemistry, University of Warwick, Coventry, CV4 7AL, U.K. 5 Department of Biology, London Centre for Nanotechnology, University College London, London WC1E 6BT, UK.

Project Organisation
Funded through the Basic Technology programme November 2008 start, duration 4 years. Includes 3 institutions (Warwick, UCL and Imperial) and 7 investigators. Crossing boundaries: PIs experts in different branches of Science (Chemistry, Physics, Biology) and Engineering (Materials, EE). Directly employs 4 PDRAs and 3 PhD students Project extends boundaries: Additional academics (a.o. Hirjibehedin, Curson, Nathan, Ryan), more than 7 PhD students and PDRAs closely linked to the project

Project Summary and Context

Combine cheap organic electronics and high performance spintronics to develop molecular spintronics with outcomes in IT and biosensing. Use expertise in small molecule film growth, magnetism, theory, optoelectronics, device engineering and spin resonance applied to biology.
Molecular Electronics OPV, OLED, Transistors Semicond. polymers and molecules Nelson, Durrant (IC), Forrest Organic Spintronics Molecular films as tunnelling layers Molecules on magn. surfaces
Xiong, Nature 04 Baibich, PRL88

Spintronics GMR, MRAM Magnetic HJ Magnetic Semiconductors Molecular Magnetism Magnetic switching, spin-crossover
Verdaguer, Science 96

Visibility and Outcomes

Key Publications and Patents
A Novel Route for the Inclusion of Metal Dopants in Silicon, Nanotechnology 21 (2010) 035304. Ultralong copper phthalocyanine nanowires with new crystal structure and broad optical absorption, ACS Nano 4 (2010) 3921-3926. Morphology and Structure Transitions of Copper Hexadecafluorophthalocyanine (F16CuPc) Thin Films, J. Phys. Chem. C 114 (2010) 1057. Theoretical modeling of exchange interactions in Cu(II)Pc onedimensional chain, Phys Rev B (2011) in press. Spin-based diagnostic of nanostructure in films of a common molecular semiconductor submitted. Patent: A Novel Route for the Inclusion of Metal Dopants in Silicon (GB0908254.6).

BT Molecular Spintronics
Unique combination of properties

Molecular powder, e.g. Prussian Blue

Applications in IT Combine magnetic centre (Q-bit) with semiconducting ring (control)

Exploit spin and magnetism in optoelectronic devices based on organometallics

N N N N
-

N Cu
2+

Applications in Biosensing Label-free detection based on specific spin relaxation

N N

Main Milestones
Nanowire film and FET Set of rules for correlation between molecular parameters and exchange couplings EPR Hamiltonian Thin film Tc above 77K Optical control of exchange interactions EPR detection of biomolecules based on antibody/antigen interactions Magneto-optic phenomenology and EPR Hamiltonian for bioassay

Further funding
Project is a platform for further funding, including EPSRC-NSFC grant in Foundations of Molecular Nanospintronics.

Engineering Application: new route to

determine local order in organic solar cells
Key issue: efficiency of organic devices strongly depends on molecular orientation. However, diffraction cannot always be applied in poorly crystallised systems. Objectives: use spin resonance lineshapes and positions to determine local order and orientation of dye molecules in test systems and apply to rationalisation of solar cells Top view of molecules on substrate g-factors observed
CuPc on glass CuPc templated
gperp g// g// gperp

Science Application: molecular magnetic

wires and films from vapour
Nanowires and films are essential for miniaturisation of spintronic device and efficient spin transport through single crystal domains

CuPc by Organic Vapour Phase Deposition

Based on molecules in a 3-zone furnace and inert carrier gas wires with new crystal structure, high flexibility and aspect ratios approaching CNTs

Film On glass Templated

B perp ( = 90) g g//

B parallel ( = 0) g// and g g

d001 1 cm
Normalised magnetisation 1.0 0.8 0.6 0.4 0.2 0.0

N2

400 nm

20 nm

B perpendicular ( = 90)

B parallel ( = 90)

Film on glass
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 Field (mT) 1 0.8 0.6 0.4 180 170 160 150 140 130 120 110

Templated
1 0.8 0.6 0.4 180 170 160 150 140 130 120 110

CuPc:C60 mixed
1 0.8 0.6 0.4 0.2 0 -0.2 -0.4 -0.6 -0.8 -1

beta wire

Orientation ()

Orientation ()

0.2 0 -0.2 -0.4 -0.6 -0.8 -1

100 90 80 70 60 50 40 30 20 10 0 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 Field (mT)

Orientation ()

0.2 0 -0.2 -0.4 -0.6 -0.8 -1

100 90 80 70 60 50 40 30 20 10 0 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 Field (mT)

alpha
0 1 2 3 4 m0H (Tesla) 5 6 7

Magnetic properties show that wires have antiferromagnetic coupling, as rationalised by theoretical calculations. High orbital overlap along long axis should mediate high anisotropic conductivity.

Increasing Tc using different transition metal derivatives

Thin films grown using organic molecular beam deposition
1.0
0.8 0.6 0.4 0.2

Unexpected benefit of BT project for energy sector: molecular spins as an inexpensive in-line quality control tool to measure mol. orientation clustering and preferential orientation with molecules perp to substrate in mixed CuPc:C60 unfavourable orientation of molecules in mixed solar cells, points to path for increased efficiency

1.5x10 1.2x10

M normalised at 7T

0.0 -0.2

0.5
-0.10 -0.08 -0.06 -0.04

-0.4 -0.6 -0.8

Ferromagnetic film with Tc ~26 K

(Oe/emu)

m0H (Tesla)
-0.02 0.00 0.02

0.04

0.06

0.08

0.10

9.0x10 6.0x10 3.0x10

0.0

-0.5

-1

-1.0 -7 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6 7

0.0 0 20 40 60 80

m0H (Tesla)

Magnetisation