Potential of Environmental Conditions

to Cause Degradation of
Photoconductive Porphyrin Nanorods
Eugenia Rose ‘20 and McKenna Finley ‘23
Lewis and Clark College
Department of Chemistry
Abstract
This study was designed to determine the role of UV irradiation in the degradation of
porphyrin nanorods, which are photoconductive materials that have the potential to be
utilized in cost-effective solar cells. Porphyrin molecules in solution were aggregated into
nanorods by the addition of solutions of hydrochloric acid and ammonium chloride salt.
Solutions containing aggregates were irradiated continuously with a 365 nm UV light source
for 168 hours, and UV-vis absorption spectra were taken at various points during that period.
Changes in the absorption spectra of the UV-irradiated samples were compared against
those of solutions stored in darkness. The absorption peaks associated with nanorods
fluctuated throughout the period for all solutions, but those under UV irradiation decreased
most significantly. The reduction of these absorption peaks indicates a decreased amount of
nanorods in solution, suggesting that UV-irradiation causes the degradation of these
structures.
Introduction
Photovoltaics are just one of many kinds of solar cells, and photovoltaics made of organic
molecules (organic photovoltaics or OPVs) are of particular interest due to the possibility of
lower production costs and the use of less toxic materials than silicon-based solar cells.
OPVs consist of conductive polymers that convert solar energy into electricity. Porphyrins
have similar structures to chlorophyll molecules of photosynthetic organisms, making them
ideal light-harvesting molecules for OPVs. Previous research has also indicated that
tetrakis(4-sulfonatophenyl)porphine (TPPS) nanorod aggregates are photoconductive,
meaning that they are able to conduct current when exposed to a light source (Schwab et al.
2004). These TPPS nanorods are also stable in the solid state, and do not degrade when
stored in darkness. In order to ensure that porphyrin nanorods will be viable OPV materials,
it is necessary to study their stability. This research focused on studying the stability of TPPS
nanorods in solution when exposed to UV light.
Schwab, A. D.; et al. Photoconductivity of Self-Assembled Porphyrin Nanorods. Nano Letters. 2004, Vol.4 No. 7, 1261-1265.
Degradation Mechanisms in OPVs
All OPVs undergo the same degradation processes. They are susceptible to a
“burn-in” period in which thermal and photochemical effects on the OPV material
cause a rapid decrease in efficiency over a short period of time (Mateker &
McGehee 2017). After this “burn-in” period, the OPV will have a slower and
steadier degradation rate until the device begins to fail. Degradation can be
caused by a variety of environmental factors, including illumination and the
introduction of oxygen and water to the OPV (Mateker & McGehee 2017). Intrinsic
factors such as the reassortment of molecules within a structure have also been
found to cause OPV degradation (Mateker & McGehee 2017).

W. Mateker and M. McGehee. Progress in Understanding Degradation Mechanisms and Improving Stability in Organic Photovoltaics. Adv. Mat. 2017, 29, 10.
Photoconductive Porphyrin Nanorods
Figure 1 shows the structure of a
TPPS monomer. Porphyrins are
tetrapyrrole macrocyclic molecules
(Schwab et al. 2003) that have the
ability to form aggregates due to the
electrostatic interactions between
the sulfonato and pyrrole groups of
separate molecules (Figure 1).
Figure 1. TPPS monomers form nanorods through
electrostatic interactions between negatively
charged sulfonato groups (in red) and positively
charged pyrrole groups (in blue).

Schwab, A. D.; et al. Porphyrin Nanorods. Phys. Chem. B. 2003, 107, 11339-11345.
Photoconductive Porphyrin Nanorods
When aggregation is
induced, these molecules
can form dimers (Figure 2)
that will continue to
aggregate, eventually
forming extended
J-aggregates. These
J-aggregates make up the
Figure 2. The proposed structure of the Figure 3. The dimers continue to stack
nanorod form of the dimer is shown here, with two TPPS into J-aggregates, and the shape of the
molecules stacked together. Adapted from: stacking results in the formation of a
molecule (Figure 3). Malatesta, R. A Study of the Formation, nanorod. Adapted from: Schwab, A. D.;
Degradation, and Morphologies of Porphyrin et al. Phys. Chem. B. 2003, 107,
Nanoaggregates. 2019. 11339-11345.
Methodology
Porphyrin J-aggregates assemble when electrolytes are introduced to solution via the addition of
either acid or salt (Schwab et al. 2003). To initiate pH-induced aggregation, hydrochloric acid was
added to TPPS in solution. NH4Cl-induced aggregation was initiated by combining an ammonium
chloride solution and TPPS in solution with a minute amount of hydrochloric acid. Identical volumes
of both solutions were added to quartz cuvettes, and the remainder of both solutions were stored in
darkness to serve as controls. Initial UV-vis spectra were acquired for the solutions in cuvettes and
the dark controls using a Vernier UV-vis spectrophotometer and Logger Pro 3.8.7. The TPPS
aggregate solutions in quartz cuvettes were sealed and placed 12.0 cm away from a Darkbeam
365nm UV flashlight in a black cardboard box. Once the flashlight was turned on, the
solution-phase TPPS aggregates were continuously irradiated with UV light for 168 hours, save for
when samples were taken to acquire UV-vis spectra. UV-vis spectra for the UV-irradiated samples
were acquired at 0 hours, 23 hours, 72 hours, and 168 hours. Spectra of the dark control solutions
were also acquired simultaneously.

Schwab, A. D.; et al. Porphyrin Nanorods. Phys. Chem. B. 2003, 107, 11339-11345.
UV-vis spectroscopy
UV-vis spectroscopy measures the
absorption of light in the visible and UV
spectrum. Porphyrin monomers have
an absorption peak at 413 nm, while
the dimer and J-aggregate (nanorod)
peaks are red-shifted because these
larger aggregates absorb longer
wavelengths of light. The normalized
UV-vis absorption spectra of the
monomer, dimer and J-aggregate
forms of TPPS are shown in the figure
to the right. Figure 4. UV-vis spectra of various forms of the porphyrins. Adapted
from: Malatesta R. A Study of the Formation, Degradation, and
Morphologies of Porphyrin Nanoaggregates. 2019.
Raman Spectroscopy
Raman spectroscopy is a
technique commonly used to
identify and characterize
substances based on their
vibrational properties. When
exposed to electromagnetic
radiation, the vibrations of a
compound change the energy of
the radiation scattered back,
causing a shift in the wavelengths
of light. Figure 5 shows the
Raman spectrum of a dried
nanorod sample, which still has a
strong signal after being stored in
the dark at ambient temperature Figure 5. Raman spectrum of a sample of TPPS nanorods dried on a glass
for over 3 years. microscope slide prepared by Lauren Heald in 2016. Spectrum acquired on
1/29/20 with a HORIBA Scientific XPlora Plus Raman Microscope and HORIBA
Scientific LabSpec 6 software.
Results: UV-irradiation of pH-induced nanorods
Figure 6. UV-vis
spectra of
pH-induced TPPS
nanorod solution
under constant UV
irradiation (A) and
dark control (B) at
various times.
Spectra acquired
with Vernier UV-VIS
Spectrophotometer
and Logger Pro
3.8.7.
A. B.
B.

UV-vis absorption peaks at 491 nm and 710 nm correspond to the nanorod form of
the TPPS. A decrease in these peaks indicates a decrease in the amount of
nanorods present in solution. The nanorods exposed to UV radiation (Figure 6A)
demonstrate a more dramatic change in these peaks than the nanorods left in
darkness (Figure 6B) over the same time period (1 week).
Results: UV-irradiation of NH4Cl-induced nanorods
Figure 7. UV-vis
spectra of
NH4Cl-induced TPPS
nanorod solution
under constant
UV-irradiation (A) and
dark control (B) at
various times.
Spectra acquired with
Vernier UV-VIS
Spectrophotometer
and Logger Pro
3.8.7.
A. B.

Similar results were observed for the NH4Cl-induced aggregates; the nanorods
exposed to UV radiation (Figure 7A) have the most significant decrease in
absorbance of all samples studied. The nanorods left in darkness (Figure 7B) do
not demonstrate the same decrease in absorbance. Although only one set of
spectra is shown here, these results were replicated in another trial.
Discussion
All nanorod solutions demonstrated changes in the UV-vis absorption of aggregate
peaks, even the solutions stored in darkness. This could indicate that there are
general fluctuations in the amount of nanorod present in solution over time,
regardless of what the solution is exposed to. Another possible explanation is that
leaving a solution for long periods of time allows the nanorods to settle, and they
are no longer suspended in solution. This would result in a lowered nanorod
absorption peak, but the quantity of nanorods present may actually be unchanged.
However, the more dramatic decreases in UV-vis absorption by the solutions
exposed to UV light cannot simply be explained by settling, so it is possible that
UV has damaging effects on the nanorods.
Future Research
Since all of our work focused on solution-phase nanorods, a possible direction for
future research would be to see if UV exposure damages solid-state (dried)
nanorods. It is also possible that reactive oxygen species in the solution were
actually causing the observed degradation, so repeating this experiment in an
oxygen-poor environment would be another useful study. Another possible
direction for future work would be to study the degradation of nanorods exposed to
light from a solar simulator, which would more accurately represent the light
exposure a solar cell would typically receive. Finally, in order to have a more
accurate baseline for comparison, it is necessary to study the fluctuations of
absorption peaks observed in the dark control solutions and account for the
possibility of nanorod settling.
Acknowledgments
We are grateful to our advisor Julio de Paula and the Lewis & Clark College
Department of Chemistry for their guidance and support during this research
process. We would also like to thank the James F. and Marion L. Miller Foundation
for additional funding.