Electron Spin Resonance

Applications in Organic Electronics

Abstract
The physical properties and functionality of organic thin films is strongly dependent on nanostructure and molecular orientation. In particular, texturing and blending enhance the performance of optoelectronic devices, leading to a rise in organic solar cell efficiencies from ~1% up to ~6%. Characterisation of such complex nanostructures is essential for both fundamental understanding and quality control, but cannot be performed by standard methods, instead requiring difficult sample preparation and/or large scale facilities such as synchrotrons. Here we introduce a new methodology to elucidate key materials properties of both model and complex molecular films - namely molecular orientation and aggregation - using electron paramagnetic resonance (EPR), a simple non-destructive technique which is available in many laboratories and can be readily implemented in factories.
gper
p

CW EPR
The Effects of Rotation and Spin Dilution
Parallel Film Orientation CuPc has been studied at length in the EPR literature [2 and references therein]. However it has never been studied in the templated phase. The templated phase allows a bulk measurement of a reasonable approximation to the single molecule spectra.
gpara

Spin Dilution Measurements

Intermolecular coupling between copper atoms causes broadening of the spectrum. Spin dilution, isomorphously replacing some CuPc with H2Pc, reduces coupling between copper atoms and thereby reduces broadening.

Organic Solar Cells

Testing C60:CuPc Thin Films
Experimental
(a)
180 165 150 135 120 105 90 75 60 45 30 15 0 250 275 300 325 350 375 400 Field (mT) 0.6 0.4 0.2 0 -0.2 -0.4 -0.6
()

Simulation
(e)
180 165 150 135 120 105 90 75 60 45 30 15 0 250 275 300 325 350 375 400 Field (mT) 0.6 0.4 0.2 0 -0.2

(a)

CuPc:C60
180 165 150 135 120 105 90 75 60 45 30 15 0 250 275 300 325 350 375 400 Field (mT) 0.6 0.4 0.2

(b)

20nm H2Pc CuPc:C60

180 165 150 135 120 105 90 75 60 45 30 15 0 250 275 300 325 350 375 400 Field (mT) 0.6 0.4 0.2 0 -0.2 -0.4 -0.6

Perpendicular Film Orientation

B field

100% templated

()

Parallel

Perpendicular

()

-0.4 -0.6

0 -0.2 -0.4 -0.6

()

(b)
180 165 150 135 120 105 90 75 60 45 30 15 0 250 275 300 325 350 375 400 Field (mT) 0.6 0.4 0.2 0 -0.2 -0.4 -0.6

(f)
180 165 150 135 120 105 90 75 60 45 30 15 0 250 275 300 325 350 375 400 Field (mT) 0.6 0.4 0.2 0 -0.2 -0.4 -0.6

The figures show the two extreme orientations of the films, parallel and perpendicular to the field. As the g value is axially symmetric these spectra allow direct readout of the g tensor and hyperfine splittings. These measurements were taken at room temperature. Also shown is an echo detected field sweep (EDFS) of the 5% sample taken at 10 K. Percentages indicate percentage of CuPc.

50% templated

()

()

(c)
180 165 150 135 120 105 90 75 60 45 30 15 0 250 275 300 325 350 375 400 Field (mT) 0.6 0.4 0.2 0 -0.2 -0.4 -0.6

(g)
180 165 150 135 120 105 90 75 60 45 30 15 0 250 275 300 325 350 375 400 Field (mT) 0.6 0.4 0.2 0 -0.2 -0.4 -0.6

Films of CuPc:C60 (with and without an underlying H2Pc layer) were prepared. A rotation pattern was measured using CW EPR (above). This can be compared to similar rotation patterns of model films, of H2Pc and CuPc both templated and non-templated, at 100% CuPc and 50% CuPc. The comparison allows us to deduce that the CuPc is forming nanoclusters, undetectable via XRD, with a molecular orientation approximately perpendicular to the film surface.

100% Non templated

()

(d)
180 165 150 135 120 105 90 75 60 45 30 15 0 250 275 300 325 350 375 400 Field (mT) 0.6 0.4 0.2 0 -0.2 -0.4 -0.6

(h)
180 165 150 135 120 105 90 75 60 45 30 15 0 250 275 300 325 350 375 400 Field (mT) 0.6 0.4 0.2 0 -0.2 -0.4 -0.6

50% Non templated

()

()

()

Towards Quantum Computing

Pulsed EPR

The spin degree of freedom of CuPc might also act as a host for quantum information. The DiVincenzo criteria [4] outline the most fundamental experimental requirements for a quantum computer; qubits, initialisability, decoherence times, universal quantum gates and readout. The first step to determine the potential of a material as a qubit is to find the decoherence times. Here we show that for the 5% spin diluted templated CuPc sample, the T1 times are of order 1 ms and T2 times of order 1 s. T1 measurements T2 Measurements Rabi Oscillations - Single Qubit Rotations

T1 times were measured via a inversion recovery pulse sequence. The temperature dependence of the T1 times imply that the the spin lattice relaxation times are not simply direct linear processes.

T2 times were measured via a Hahn echo pulse sequence.

Rabi oscillations were measured by varying the pulse length. The frequencies scale, as expected, as the square root of the microwave power.

The research team

For information on ESR, contact Dr Chris Kay, Institute of Structural & Molecular Biology and LCN, c.kay@ulc.ac.uk Current LCN collaborators on this project: Prof Gabriel Aeppli (UCL), Prof Andrew Fisher (Physics, UCL), Dr Sandrine Heutz (Materials, Imperial), Dr Gavin Morley (Physics, UCL). PDRAs: Dr Marc Warner (Physics, UCL), Dr Wei Wu (Chemistry, Imperial).