Measuring electric field dependent photodegradation and
recovery of disperse orange 11 dye doped polymer thin films
using photoconductivity and digital imaging microscopy
Benjamin Anderson, Sheng Ting Hung, and Mark G. Kuzyk.
a
Department of Physics and Astronomy, Washington State University, Pullman, WA
99164-2814
ABSTRACT
One of the limiting factors of optical devices for space applications is photodamage from high intensity light
and radiation. Dye doped polymers offer many advantages in device design but are susceptible to photodamage,
especially due to high intensity UV radiation. Several organic dyes have been observed to self heal after pho-
todegradation. We seek to understand the underlying mechanism with the goal of designing materials that are
more robust to photodegradation. We test the hypothesis that photodegradation is due to charge injection into
the polymer and healing due to recombination using photoconductivity and imaging measurements of disperse
orange 11(DO11) doped into PMMA.
Keywords: Photocharge ejection and recombination, photo damage, self healing, organic dyes, photoconduc-
tivity
1. INTRODUCTION
Organic dyes and polymers find wide uses in many different fields including photolithography, dye lasers, fiber
optics, organic light emitting diodes, optical data storage, etc.
1–5
One problem with using organic dye-doped
polymers in optical devices is photodegradation. Much research has been performed to understand photodegra-
dation in dye-doped polymers.
6, 7
Furthermore, over the past two decades, an exciting effect has been discovered
in which a wide variety of organic-dye doped polymers show self healing after being photodegraded.
8–16
Currently
the actual mechanism of self healing is unknown, but several mechanisms have been proposed.
One of the proposed mechanisms of photo decay and self healing in dye-doped polymers is that of charge
ejection and recombination.
17
The proposed mechanism assumes when a dye molecule is damaged by intense
light it ejects a charge into the polymer; the charge is free to move and possibly get trapped. Self healing occurs
when charges eventually migrate back and recombines with a damaged molecule, returning it to its original
state. This is consistent with our observation that the organic dyes of interest degrade irreversibly in solution,
but recover in a polymer matrix.
9, 10
Without the polymer and the trap sites, the photo ejected charge is free to
leave and will not recombine with the damaged molecule.
An obvious consequence of the model of charge ejection and recombination is that the recovery will be
affected by an applied electric field. To test the charge ejection and recombination mechanism, we developed an
experiment with two probes of decay and recovery. The first builds on our previous work with digital imaging
microscopy
15, 16
by using the same apparatus, now applying an electric field while imaging; the second method is
a more direct electrical measurement utilizing photoconductivity as a measure of decay and recovery if charged
products are indeed formed.
2. PHOTOCONDUCTIVITY THEORY
The process of photoconductivity in dye-doped polymers is a far more complicated matter than the usual exem-
plar of semiconductors. Semiconductors have a periodic structure, which leads to a predictable band structure
used to describe their conductivity and photoconductivity.
18, 19
Dye-doped polymers have varying degrees of
conductivity and photoconductivity, but one cannot simply describe the processes using a simple periodic band
structure. Although dye-doped polymers do have a band structure, due to their random nature the bands are
Invited Paper
Nanophotonics and Macrophotonics for Space Environments VI, edited by Edward W. Taylor,
David A. Cardimona, Proc. of SPIE Vol. 8519, 85190H · © 2012 SPIE
CCC code: 0277-786/12/$18 · doi: 10.1117/12.929776
Proc. of SPIE Vol. 8519 85190H-1
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