Optical Materials 58 (2016) 93e101

Contents lists available at ScienceDirect

Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Photoluminescence analysis of a polythiophene derivative:

Concentration and temperature effects
J. Castrellon-Uribe*, M. Güizado-Rodríguez, R. Espíndola-Rivera

n en Ingeniería y Ciencias Aplicadas, CIICAp, (IICBA), Universidad Auto
Centro de Investigacio
noma del Estado de Morelos, UAEM, Av. Universidad No. 1001,
Col. Chamilpa, C.P. 62209 Cuernavaca, Morelos, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: In this work, the photoluminescence properties of a PA copolymer, which is a polythiophene derived
Received 30 January 2016 from 3-OT and (S)-(-)-1-(4-nitrophenyl) pyrrolidin-2-il) methyl 2-(thiophen-3-yl) acetate, were inves-
Received in revised form tigated. The optical response of the copolymer dissolved in a toluene solution and of the copolymer film
22 March 2016
under the optical excitation was analyzed. Besides, the temperature dependence of photoluminescence
Accepted 26 March 2016
(PL) of the PA copolymer (solution and film) was examined. The PL behavior of the solution-phase
copolymer (diluted and concentrated solutions) under 365 nm (UV light) excitation is reported. More-
over, the copolymer films were obtained using the spin coating technique. The PL of the copolymer films
Keywords:
Polythiophene
under 488 nm (blue light) irradiation was studied at different excitation powers. Finally, we examined
Photoluminescence the PL signal temperature dependence of the copolymer film. We determined that the maximum PL
Fluorescence quenching signal peak of the copolymer corresponds to 626 nm and has a temperature sensitivity of approximately
Temperature sensor 11
103/ C, with a minimum ascending and descending temperature hysteresis between 22  C and
50  C.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction triggers the emission of a photon with a longer wavelength (less

energetic). Currently, the luminescence properties of conjugated
The development of new materials with non-linear optical polythiophenes are of considerable interest due to their potential
properties (NLO) has been one of the main objectives of research applications in light-emitting diodes (LEDs) [16,17], organic solar
and development in the field during the past few decades due to cells [18e21] and optical chemical sensors [22e25].
their important applications primarily in photonics [1]. In recent In this work, the photoluminescence properties of the PA
years, conducting polymers (CPs), such as polypyrrole (PPy), poly- copolymer (solution and film) under optical excitation were
aniline (Pani), polythiophene (PTh) and their derivatives, have been investigated. First, the synthesis of the novel copolymer was per-
investigated because of their chemical and electro-optical proper- formed and was reported in Ref. [26]. Next, the absorbance of the
ties for the development of gas and chemical sensors [2e4]. The CPs copolymer dissolved in a toluene solution at different concentra-
are synthesized using chemical or electrochemical processes, and tions was measured and their photoluminescence was analyzed.
their molecular chain structure can be conveniently modified via Besides, the photoluminescence signal temperature dependence of
copolymerization or structural derivations. Currently, the research the copolymer in a toluene solution was examined. Later, the
has been focused on the thiophene-based polymers due to their copolymer films were obtained using the spin coating technique.
structural versatility, solubility upon functionalization and envi- Next, the copolymer film was optically excited at 488 nm, and the
ronmental stability. In addition, the functionalized polythiophenes photoluminescence signal that was generated at 620 nm was
combine interesting nonlinear optical (NLO) [5e10] and photo- monitored at different optical powers. Moreover, the films were
luminescence (PL) properties [11e15]. Fluorescence is a photo- exposed to different temperatures (20  Ce50  C) under a constant
luminescence in which the molecular absorption of a photon optical excitation, and the PL signal variations of the films were
monitored to determine their optical sensitivity. Finally, a
morphologic study of the copolymer films was performed to
* Corresponding author. determine the surface damage due to laser radiation and
E-mail addresses: jcastrellon@uaem.mx (J. Castrellon-Uribe), marisolguizado@ temperature.
uaem.mx (M. Güizado-Rodríguez).

http://dx.doi.org/10.1016/j.optmat.2016.03.049
0925-3467/© 2016 Elsevier B.V. All rights reserved.
94 J. Castrellon-Uribe et al. / Optical Materials 58 (2016) 93e101

2. Experimental procedure First, the optical absorbance of the copolymer dissolved in toluene
at different concentrations was measured using a tungsten halogen
2.1. Synthesis and physicochemical characterization of the PA light source. The concentrations of the copolymer were:
copolymer [0.005e0.025 mg/mL] and [0.5e2.5 mg/mL] of the diluted and
concentrated solutions, respectively. Then, the absorption spectra
The PA copolymer, structure in Fig. 1, was synthesized according were monitored and analyzed at room temperature in the
to the previously reported polymerization procedure [26]. This 250e900 nm wavelength region.
procedure involves an oxidative polymerization of 3- Subsequently, in a second optical experiment, the copolymer
octylthiophene and (S)-(-)-1-(4-nitrophenyl) pyrrolidin-2-il) photoluminescence in a toluene solution was investigated. A UV
methyl 2-(thiophen-3-yl) acetate in the chloroform and nitro- lamp with a 4 W output was used to irradiate the solution-phase
methane solution of FeCl3. Soluble yield was 15%, monomer ratio copolymer. The PL signal was observed up to approximately
was 88% for 3-OT and 12% for functionalized thiophene, molecular 580 nm (yellow light) when the copolymer was excited using a
weight was Mn ¼ 11,000 g/mol, Mw ¼ 117,000 g/mol, PDI ¼ 10.6. 365 nm wavelength. The PL signal of different copolymer concen-
Thermal stability: Td ¼ 474  C, weight loss ¼ 71%. The 1H NMR trations (diluted and concentrated solutions) was monitored and
signals, Fig. 1, showed the configurations of diads (HT ¼ 68%, analyzed at room temperature. Later, in a third optical experiment
HH ¼ 32%) and triads (HT-HT ¼ 50%, TT-HT ¼ 15%, HT-HH ¼ 18%, TT- the PL signal behavior of the solution-phase copolymer, when it
HH ¼ 17%). 1H NMR (200 MHz, CDCl3, TMS), 3-octylthiophene: was exposed to different temperatures (20  Ce50  C) was investi-
d ¼ 6.98 (H40 ), 2.79, 2.60 (Ha), 1.66, 1.26, 0.87, 0.07 (Hbq). Func- gated. The fluorescence spectra were recorded using a spectrom-
tionalized thiophene: d ¼ 8.06 (H17,19), 7.00 (H4), 6.60 (H16,20), eter (Ocean Optics, Dunedin, Florida, USA).
3e4.5 (H6,9,10,12), 2.0 (H13,14) [26]. The physicochemical properties
of the PA copolymer, such as regioregularity (diads and triads),
molecular weight distribution (Mn and Mw) and thermal proper- 2.2.2. PA copolymer in films
ties (Td), are similar to those found in the PT that was synthesized Additionally, the photoluminescence properties of the PA
using the same regioselective method [5,10]. The synthesized PA copolymer film were investigated. First, a PA copolymer toluene
copolymer has a low molecular weight and a large polydispersity. solution (60 mg/mL) was used to deposit thin films via spin coating
Additionally, in the copolymer, the incorporation of functionalized at approximately 5000 rpm on glass substrates (corning glass). The
thiophene, with a pushepull chromophore as pendant group, is films were characterized using AFM (nano scope IV multimode
considerable (12%). Finally, the polythiophene derivative has a good scanning probe microscope). Then, the absorption spectra of the
thermal stability [26]. films with thicknesses of approximately 200 nm for a concentration
of 60 mg/mL were measured at room temperature for the wave-
length interval from 300 nm to 650 nm. After that, the PL of the
2.2. Optical measurements copolymer film was measured. The generated PL signal was
observed up to approximately 630 nm (red light) when the films
2.2.1. PA copolymer in a toluene solution were excited with a laser at 488 nm (blue light). Likewise, the PL
To investigate the photoluminescence properties of the PA behavior was studied at different excitation optical powers
copolymer in a toluene solution, the following procedure was used. (5e20 mW). The PL signal of the films was analyzed at room

Fig. 1. 1H NMR spectrum of PA copolymer and its structure.

 J. Castrellon-Uribe et al. / Optical Materials 58 (2016) 93e101 95

temperature, and the fluorescence spectra were recorded using a

spectrometer (Ocean Optics, Dunedin, FL, USA).
To investigate the copolymer film PL response when the
copolymer was exposed to different temperatures, a third experi-
ment was implemented. Specifically, new copolymer films were
obtained using the spin coating technique. Then, the laser with a
488 nm wavelength was employed to irradiate (with a constant
optical power) the films and to excite the fluorescence signal. A
thermoelectric cooler was used to control temperature changes on
the films, and a thermocouple monitored the surface temperature.
Then, the copolymer film fluorescence spectrum was monitored
when it was exposed to different temperatures (22  Ce50  C).
Additionally, the absorption spectra of the copolymer film were
measured in the same temperature range.

3. Experimental results and discussion

3.1. UVevis and photoluminescence of the PA copolymer in a

toluene solution
Fig. 3. Measured absorption spectrum of the PA copolymer in a toluene solution at
Fig. 2 depicts the absorbance of the copolymer dissolved in a different concentrations (concentrated solutions).
toluene solution at different concentrations from 0.005 mg/mL to
0.025 mg/mL (dilute solution). The absorption spectrum is Additionally, the absorption spectrum broadening towards
observed from 300 nm to 500 nm and exhibits two maximum longer wavelengths (green color) and the wavelength shift of
peaks at 388 nm and 436 nm that correspond to p / p and n / p approximately 38 nm for the concentration range of 0.5e2.5 mg/
transitions, respectively. The copolymer with a concentration of mL is observed.
0.005 mg/mL has an absorbance of 0.14. Whereas, at a concentra- Conductive polymers, such as polythiophene (PTh), and their
tion of 0.025 mg/mL, the absorbance is 0.7 when measured at a derivatives combine non-linear optical and photoluminescence
388 nm wavelength. The figure shows that with an increase in the properties. Typically, when polythiophenes are excited with pho-
copolymer solution-phase concentration, an increment in the op- tons of particular energy, the luminophores are promoted toward a
tical absorbance is detected. higher energy level. The excited electron returns to the unexcited
Likewise, the absorbance of the copolymer dissolved in a ground state via a combination of radiative and non-radiative
toluene solution at concentrations between 0.5 mg/mL and 2.5 mg/ processes that arise due to several different mechanisms. Emis-
mL (concentrated solution) is shown in Fig. 3. The absorption sion occurs through the radiative processes called luminescence.
spectrum shows an approximately constant maximum absorbance The transition from the excited level to the electronic fundamental
of 3.4 between 300 nm and 550 nm wavelengths at a concentration state occurs through the emission of photons with a longer wave-
of 2.5 mg/mL (see Fig. 3). Nevertheless, compared with the dilute length (lower energy) compared to the excitation wavelength. The
solution results, minimum absorbance changes are observed be- radiation transition from the lowest excited singlet state to the
tween different concentrations. This suggests that the absorbance ground state is called fluorescence. In general, fluorescence in-
is close to saturation, which may be related to the high copolymer tensity is determined primarily by the solution-phase copolymer
concentration (concentrated solution), and, consequently, the concentration and other parameters. Additionally, the poly-
behavior does not obey the BeereLambert law. thiophene side chain plays an important role in fluorescence
quenching processes, which are utilized in chemical sensing ap-
plications [15,22].
Fig. 4 depicts photoluminescence spectra of the PA copolymer
dissolved in a toluene solution at different concentrations (dilute
solutions). The PL signal peak maximum of the copolymer was
measured at 570 nm (visible light: yellow) when the copolymer
was excited using 365 nm UV radiation. The Stokes shift is
approximately 190 nm, which indicates that the PA copolymer was
well-dispersed in toluene. When the copolymer solution concen-
tration is increased, the overall PL spectrum intensity increases
without spectrum shape distortion or peak energy position alter-
ations, as seen in Fig. 4. Thus, when the solution-phase copolymer
is optically excited, a greater number of photons are emitted as a
function of concentration between 0.005 and 0.025 mg/mL.
However, the PL spectra of the copolymer dissolved in a toluene
solution at different concentrations (concentrated solutions) are
shown in Fig. 5. The PL signal has a maximum peak centered at
580 nm at a concentration of 0.5 mg/mL. But at a concentration of
2.5 mg/mL, the maximum peak position is approximately 610 nm
when the solution-phase copolymer is excited at 365 nm wave-
Fig. 2. Measured absorption spectrum of the PA copolymer in a toluene solution at
length. When the concentration is increased to 2.5 mg/mL, the
different concentrations (dilute solutions). maximum peak in the fluorescence spectrum shows a spectral
96 J. Castrellon-Uribe et al. / Optical Materials 58 (2016) 93e101

essence, this is a re-absorption effect, which is a radiative single-

tesinglet energy transfer process. Because the absorption and
fluorescence spectra of the solution-phase copolymer overlap be-
tween approximately 525 nm and 800 nm (see Fig. 6), the primary
emitted photons in this region undergo energy transfer processes
(singletesinglet) to other nearby ground state molecules, which
causes fluorescence intensity quenching.
Additionally, when the polymer concentration decreases from
2.5 mg/mL to 0.5 mg/mL, the fluorescence signal maximum peak
shows a spectral displacement from 610 nm to 580 nm with a
wavelength shift of approximately 30 nm, and its intensity in-
creases, as observed in Fig. 6. Similarly, when the absorbance
gradually decreases as a function of polymer concentration, an
absorption spectrum shift towards shorter wavelengths (blue co-
lor) is observed, and the fluorescence intensity increases, as
observed in Fig. 6.
Likewise, the non-radiative energy transfer process (the Fo€rster
type) may play a significant role in fluorescence self-quenching of
the copolymer that is dissolved in a toluene solution at high con-
Fig. 4. Measured photoluminescence spectrum of the PA copolymer in a toluene so-
centrations. The energy transfer process should reduce the overall
lution at different concentrations (dilute solutions).
emission spectral intensity at a higher concentration without dis-
torting the spectral shape or the peak energy positions. Neverthe-
displacement from yellow towards orange color with a wavelength €rster type energy transfer may affect the copolymer
less, the Fo
shift of approximately 30 nm, and the intensity decreases (see fluorescence lifetime value at high concentrations.
Fig. 5). The photoluminescence intensity decrease is related to the
fluorescence quenching processes. 3.2. Temperature dependence of photoluminescence the solution-
In general, the fluorescence quenching processes involves two phase copolymer
chemical species, a fluorophore and a quencher. A fluorophore is a
chemical species that, when excited, emits a fluorescence signal. A Furthermore, we investigated the photoluminescence signal
quencher is a chemical species that reduces the fluorophore fluo- temperature dependence of the PA copolymer dissolved in a
rescence signal. Typically, fluorescence intensity is proportional to toluene solution. Two different concentrations of the PA copolymer
the concentration of fluorophores within a reasonable concentra- were selected to study the behavior of luminescence spectra when
tion range. However, at high fluorophore concentrations, the pro- the copolymer was exposed to temperature changes. The concen-
portionality is no longer satisfied because the collisional quenching trations of the copolymer were 0.015 mg/mL and 1.5 mg/mL, dilute
between fluorophore molecules appears. Self-quenching is a spe- and concentrated solution, respectively. A UV lamp with a 4 W
cial type of fluorescence quenching in which the fluorophore and output was used to irradiate the solution-phase copolymer.
quencher molecules are the same. Fig. 7 shows the PL signal behavior of the solution-phase
From Fig. 5, the fluorescence self-quenching effect is attributed copolymer when it was exposed to different temperatures
to the (a) inner filter effect and to the (b) non-radiative singlete (20  Ce50  C). The PL signal variation was monitored at 570 nm
singlet energy transfer (the Fo €rster type fluorescence resonance when the copolymer (dilute solution) was excited using 365 nm UV
energy transfer) processes [27,28]. The inner filter effect distorts radiation. Additionally, photos of the solution-phase copolymer to a
the emission spectrum shape and the peak energy positions. In concentration of 0.015 mg/mL, a) without UV excitation (trans-
parent color), and b) under UV irradiation (bright yellow color) are
shown in the inset of Fig. 7.

Fig. 6. Overlapping of the absorption (black line) and PL (blue line) spectra of the PA
Fig. 5. Measured photoluminescence spectrum of the PA copolymer in a toluene so- copolymer (concentrated solutions). (For interpretation of the references to color in
lution at different concentrations (concentrated solutions). this figure legend, the reader is referred to the web version of this article.)
 J. Castrellon-Uribe et al. / Optical Materials 58 (2016) 93e101 97

increasing the entropy of the system. This behavior has been

studied in other systems and reported in the literature [30,31].
On the other hand, considering that the temperature sensitivity
of the PA copolymer in the solution-phase is evaluated as the ratio
of the change in intensity to the increase in its temperature DTso-
lution. Then, we observed a greater sensitivity to temperature
changes for the copolymer with a concentration 0.015 mg/mL in
comparison with copolymer with a 1.5 mg/mL concentration for the
same temperature interval.

3.3. Photoluminescence of the PA copolymer films

The photoluminescence of copolymer films, which are approx-

imately 200 nm thick, that were deposited on glass substrates
(corning glass) via the spin coating technique at a concentration of
60 mg/mL was investigated. Fig. 9 depicts the copolymer film
absorbance. Also, a photo of the PA copolymer film deposited on a
glass substrate by spin coating technique (60 mg/mL) is shown in
the inset of Fig. 9. The absorbance spectrum exhibits a broad ab-
Fig. 7. Photoluminescence spectra of the PA copolymer in a toluene solution sorption band with a maximum peak centered at 436 nm with a
(0.015 mg/mL) excited at 365 nm to different temperatures. a) solution-phase copol- blue-shifted absorption. Thus, the films were excited using 488 nm
ymer, and b) photoluminescence of the copolymer under UV irradiation. wavelength, and the photoluminescence signal was monitored.
We observed that the main differences between the copolymer
film absorption spectra (Fig. 9) and the solution-phase copolymer
Likewise, Fig. 8 depicts the PL signal behavior of the solution-
diluted solutions (Fig. 2) are the spectrum broadening to longer
phase copolymer for a concentration of 1.5 mg/mL when the
wavelengths (red color) with a slightly higher amplitude and the
copolymer was exposed to different temperatures (20  Ce50  C).
peak absorbance at 436 nm, which corresponds to n / p
The PL signal variation was monitored at 600 nm when the
transition.
copolymer (concentrate solution) was excited using 365 nm UV
The copolymer film normalized photoluminescence spectra are
radiation.
shown in Fig. 10. The copolymer PL signal behavior was investi-
In addition, photos of the solution-phase copolymer for a con-
gated when the copolymer was irradiated with an argon laser at
centration of 1.5 mg/mL, a) without UV excitation (red color), and b)
488 nm with different optical excitation powers of 5 mWe18 mW.
under UV irradiation (bright orange color) are shown in the inset of
A large Stokes shift of approximately 190 nm is observed for the
Fig. 8.
copolymer film, which is comparable to the shift obtained with a
When the solution-phase copolymer was exposed to tempera-
solution-phase copolymer. The PL maximum peak of the solution-
ture changes, a decrease in the PL signal was observed. The PL in-
phase copolymer was measured up to approximately 580 nm
tensity decrease is related to the fluorescence quenching processes.
(yellow-shift). Whereas, for the copolymer film, the PL maximum
This means that the excimer fluorescent population undergoes
peak was measured up to 626 nm (red-shift). This shows that there
signal changes due to thermal-quenching processes. In addition, it
is a difference in the Stokes shift of approximately 50 nm between
is known that when a polymer absorbs heat, the thermal energy
the two polymer phases (solution and film).
usually causes vibration and rotation of the chain molecules
In our experiments, the fluorescence intensity in the copolymer
film is lower than in the corresponding solution-phase copolymer.

20C
1.0
50C

0.8
Normalized PL

0.6
a) b)

0.4

0.2

0.0
400 500 600 700 800 900
Wavelength [nm]
Fig. 8. Photoluminescence spectra of the PA copolymer in a toluene solution (1.5 mg/
mL) excited at 365 nm to different temperatures. a) solution-phase copolymer, and b) Fig. 9. Measured absorbance spectrum of the PA copolymer thin film. a) Photo of the
photoluminescence of the copolymer under UV irradiation. PA copolymer film deposited by spin coating technique (60 mg/mL).
98 J. Castrellon-Uribe et al. / Optical Materials 58 (2016) 93e101

488 nm at different optical powers. The PL intensity varies

approximately linearly with the optical power of excitation from
5 mW to 18 mW, and there is a nearly linear increase in y-intercepts
with a ratio of approximately 5.3%/mW. The optical response linear
fit shows slight variations of the PL signal at different excitation
powers. The PL signal variation is associated with inhomogeneous
distribution and thickness of the PA copolymer film on the surface
of the corning glass when the PA copolymer film was deposited
using the spin coating technique.

3.4. Temperature dependence of photoluminescence of the PA

copolymer films

Furthermore, we investigated the photoluminescence signal

temperature dependence of the copolymer film, and we evaluated
its potential as a temperature sensing material.
First, the absorption spectra of the copolymer film were
measured when it was exposed to different temperatures (see
Fig. 12). The absorption spectrum is observed from 300 nm to
550 nm and exhibits temperature independence in the range of
Fig. 10. Measured photoluminescence spectra of the PA copolymer thin film excited at
488 nm a) Photo of the PA copolymer film deposited by spin coating technique (60 mg/ 20  Ce50  C.
mL) under 488 nm (blue light) irradiation. (For interpretation of the references to color Likewise, Fig. 13 shows the PL spectrum behavior of the copol-
in this figure legend, the reader is referred to the web version of this article.) ymer film that was measured when the copolymer was excited at
488 nm under a constant optical power of 10 mW and exposed to
different temperatures (22  Ce50  C).
Typically, the liquid-phase luminescence intensity is greater than
Fig. 14 shows the PL signal behavior of the copolymer film when
the solid-phase luminescence intensity. In solution, the distance
it was exposed to different temperatures from 22  C to 50  C. The PL
between neighboring molecules is too large to allow intermolecular
signal variation was monitored at 626 nm when the film was
interaction. However, in a film the distance is small enough for the
excited at 488 nm under a constant optical power of 10 mW at
excitation energy transfer (EET) to occur. There are two primary
ascending and descending temperatures. When the copolymer film
factors that determine the probability that the EET may occur: 1)
was exposed at different temperatures, an increase in the PL signal
the distance R between the donor and acceptor molecules and 2)
was observed due to thermal excitation of luminophores that are
the overlap between the fluorescence (donor) and absorption
responsible for the emission of photons as fluorescence (see
(acceptor) spectra. Additionally, the collisional quenching effect
Fig. 13).
contributes to the luminescence intensity decrease of the solid-
It is worth mentioning that the temperature increase of the PA
phase copolymers.
copolymer film increased its fluorescence intensity. This implies
Nevertheless, the measured copolymer film fluorescence signal
that the excimer fluorescent population does not undergo signifi-
gradually increased without showing self-quenching. Furthermore,
cant signal changes due to thermal-quenching processes. However,
the spectral shape did not distort and the energy peak position did
this behavior is in contrast with other fluorescent systems that are
not shift when the films were irradiated at 488 nm at different
reported in the literature, in which the decay times and intensities
excitation optical powers (see Fig. 10).
almost invariably decrease with an increase in temperature due to
Fig. 11 shows the optical response of the copolymer film that
thermally activated quenching processes [30,31]. Nevertheless, the
was measured at 626 nm when the copolymer film was excited at

Fig. 11. Photoluminescence response of the PA copolymer film at different excitation Fig. 12. Measured absorbance spectra of the PA copolymer thin film to different
optical powers. temperatures.
 J. Castrellon-Uribe et al. / Optical Materials 58 (2016) 93e101 99

h  i
DI I ðl; DTÞ=I l; Tref
s¼ ½1= C (1)
DTfilm

where I(l, DT) is the PL signal measured at 626 nm as a function of

temperature, and I(l,Tref) is the PL signal at the reference temper-
ature. DTfilm is the temperature change in the copolymer film. The
sensitivity of the copolymer that was evaluated as a temperature
sensing material was approximately 11
103/ C when monitored
at a 626 nm wavelength. We conclude that the temperature
sensitivity of the copolymer film is comparable to the sensitivity
obtained for the temperature sensors based on organic fluorescent
dyes [31] and luminescent molecular thermometers [32].

3.5. Morphology analysis of the PA copolymer films

In our investigation, a morphologic study of the PA copolymer

films was performed to determine the surface damage due to
simultaneous exposure to laser radiation and temperature. Fig. 15
Fig. 13. Photoluminescence spectra of the copolymer film excited at 488 nm to shows atomic force microscopy (AFM) images of the surface
different temperatures. morphology of polymer thin films that were deposited via spin
coating under different experimental conditions. Fig. 15 shows the
surface morphology of the a) PA copolymer film as the reference
emission intensity increase due to temperature increase has been
image, b) the surface morphology after exposure at 50  C for 5 h
observed in some luminescent polymeric molecules [29].
and c) the surface morphology after irradiation at 488 nm wave-
The slope of the PL response to temperature of the PA copolymer
length with 16 mW for 5 h. The roughness (Rq) of the reference PA
film is z 9.475
103/ C and 10
103/ C for the ascending and
copolymer thin film was 2.29 nm. The roughness (Rq) of the
descending temperatures, respectively, in the range of 22  Ce50  C.
polymer film after the temperature exposure was 3.81 nm. How-
We observe that the PL response varies approximately linearly with
ever, the roughness (Rq) was 4.64 nm of the film that was exposed
temperature. Additionally, in all optical measurements that were
to temperature and was also irradiated. The average film thickness
performed with the PA copolymer films, the obtained results were
that was determined using AFM was approximately 200 nm. The
consistent. Nevertheless, we observed a hysteresis error when the
roughness increased when the PA copolymer thin film was exposed
optical measurements were acquired at the same time as the
to 50  C and after it was irradiated at a 488 nm wavelength.
temperature was ascending and descending. This error could be
Additional grains of approximately 40 nm appeared and made the
associated with the inhomogeneous distribution and thickness of
surface irregular. However, this effect is small. In general, it is
the copolymer film on the surface of the corning glass when it was
possible to say that the polymer film is stable, as indicated by its
deposited.
thermal properties (Td ¼ 474  C).
The temperature sensitivity of the PA copolymer film was
evaluated as the ratio of the change in intensity ratio to the increase
in its temperature DTfilm. We use the following expression to 4. Conclusions
evaluate the sensitivity of the copolymer film as a temperature
sensor: This article has shown experimental results of the photo-
luminescence properties of the PA copolymer, which is a poly-
thiophene derived from 3-OT and (S)-(-)-1-(4-nitrophenyl)
pyrrolidin-2-il) methyl 2-(thiophen-3-yl) acetate when it is opti-
cally excited. The PL signals of the solution-phase copolymer at
concentrations of 0.005e0.025 mg/mL and 0.5e2.5 mg/mL (diluted
and concentrated solutions, respectively) were investigated. The
fluorescence signal for dilute solutions was measured up to
approximately 580 nm with a gradual increase in intensity as the
concentration increased. However, a decrease in intensity was
observed for concentrated solutions due to fluorescence self-
quenching effects.
The temperature dependence of photoluminescence of the
solution-phase copolymer was investigated. A decrease in the PL
signal was observed for 0.015 mg/mL and 1.5 mg/mL concentrations
due to fluorescence thermal-quenching processes.
Additionally, copolymer films were obtained using the spin
coating technique. The copolymer film was optically excited at
488 nm, and the photoluminescence signal that was generated at
620 nm was monitored at different optical powers in the range of
5e18 mW. The measured fluorescence intensity gradually
increased without showing self-quenching, spectral shape distor-
Fig. 14. Optical response to the temperature changes of the PA copolymer thin film tion, or the energy peak position shifts when the films were irra-
deposited using the spin coating technique (60 mg/mL). diated at 488 nm at different optical excitation powers.
100 J. Castrellon-Uribe et al. / Optical Materials 58 (2016) 93e101

Fig. 15. Atomic force microscopy images of the surface morphology of the PA copolymer films that were chemically deposited on a glass substrate using the spin coating technique.
(a) The reference PA copolymer film. (b) The PA copolymer films after the exposure to 50  C. c) The PA copolymer films after being irradiated at 16 mW.

Finally, the copolymer film was exposed to different tempera- Mat. 17 (2008) 243e254.
[7] H.E. Ouazzani, K. Iliopoulos, M. Pranaitis, O. Krupka, V. Smokal, A. Kolendo,
tures, and its PL signal was monitored to determine its optical
B. Sahraoui, Second and third-order nonlinearities of novel push-pull azo-
sensitivity. We determined that the maximum photoluminescence benzene polymers, J. Phys. Chem. B 115 (2011) 1944e1949.
signal peak of the copolymer films corresponded to 626 nm and [8] I. Papagiannouli, K. Iliopoulos, D. Gindre, B. Sahraoui, O. Krupka, V. Smokal,
had a temperature sensitivity of approximately 11
103/ C with a A. Kolendo, S. Couris, Third-order nonlinear optical response of push-pull
azobenzene polymers, Chem. Phys. Lett. 554 (2012) 107e112.
minimum hysteresis for ascending and descending temperatures [9] N. Liaros, S. Couris, L. Maggini, F. De Leo, F. Cattaruzza, C. Aurisicchio,
for the range from 22  C to 50  C. D. Bonifazi, NLO response of photoswitchable azobenzene-based materials,
We concluded that the PA copolymer film used as a temperature ChemPhysChem. 14 (2013) 2961e2972.
[10] M. Cha
vez-Castillo, A. Ledesma-Jua
rez, M. Güizado-Rodríguez, J. Castrellon-
sensing material showed high optical sensitivity and good repeat- Uribe, G. Ramos-Ortiz, M. Rodríguez, J.L. Maldonado, J.A. Guerrero-Alvarez,
ability for the ascending and descending temperature for the range V. Barba, Third-order nonlinear optical behavior of novel polythiophene de-
of 22e50  C. Moreover, the copolymer temperature sensitivity is rivatives functionalized with disperse red 19 chromophore, Int. J. Polym. Sci.
2015 (2015) 1e10. Article ID 219361.
comparable to the sensitivity obtained for the temperature sensors [11] N. Somanathan, S. Radhakrishanan, Optical properties of functionalized pol-
based on organic fluorescent dyes, such as rhodamine, and lumi- ythiophenes, Int. J. Mod. Phys. B 19 (2005) 4645e4676.
nescent molecular thermometers. [12] X. Zhao, X. Hu, L.H. Gan, Photoluminescent behavior of poly(3-
hexylthiophene) derivatives with a high azobenzene content in the side
chains, Polym. Adv. Technol. 16 (2005) 370e377.
Conflict of interests [13] C.G. Wu, Y.C. Lin, C.E. Wu, P.H. Huang, Synthesis and photophysics of new
highly luminescent poly(alkylthiophene) derivatives with pyridine in the
backbone, Polymer 46 (2005) 3748e3757.
The authors declare that there is no conflict of interests [14] R. Cagnoli, A. Mucci, F. Parenti, L. Schenetti, M. Borsari, A. Lodi, G. Ponterini,
regarding the publication of this paper. A poly(alkylsulfany) thiophene functionalized with carboxylic groups, Poly-
mer 47 (2006) 775e784.
[15] J. Maiti, S.K. Dolui, Photoluminescence properties of poly(thiophene-3yl-acetic
Acknowledgments acid 8-quinolinyl ester) in solution and in acid medium, J. Lumin 129 (2009)
611e614.
Authors thank A. Soto-Quintero for the valuable assistance in [16] L. Akcelrud, Electroluminescent polymers, Prog. Polym. Sci. 28 (2003)
875e962.
preparing the polymer. Additionally, A. Soto-Quintero and R. [17] S.K. Ahn, T. Ban, P. Sakthivel, S.H. Jin, Y.S. Gal, J.H. Lee, Synthesis and char-
Espíndola-Rivera are grateful for their scholarship support from the acterization of novel crosslinkable poly(propylene-dioxythiophene) deriva-
PROMEP/103.5/07/2674 project. tive as a buffer layer for organic light-emitting diode applications, Macromol.
Res. 20 (2012) 459e464.
[18] E.C. Chang, C.I. Chao, R.H. Lee, Enhancing the efficiency of MEH-PPV and PCBM
References based polymer solar cells via optimization of device configuration and pro-
cessing conditions, J. Appl. Polym. Sci. 101 (2006) 1919e1924.
[1] H.S. Nalwa, Handbook of Advanced Electronic and Photonic Materials and [19] W.H. Chen, T.H. Lee, M.T. Su, W. Lee, Electro-optical properties of photovoltaic
Devices, first ed., vol. 10, Academic Press, New York USA, 2001. cells based on P3OT-liquid-crystal and P3OT-nanomaterial blends, J. Chin.
[2] H. Bai, G. Shi, Gas sensors based on conducting polymers, Sensors 7 (2007) Chem. Soc. 57 (2010) 1172e1175.
267e307. [20] H.J. Jhuo, P.N. Yeh, S.H. Liao, Y.L. Li, Y.S. Cheng, S.A. Chen, Review on the recent
[3] U. Lange, N.V. Roznyatovskaya, V.M. Mirsky, Conducting polymers in chemical progress in low band gap conjugated polymers for bulk hetero-junction
sensors and arrays, Anal. Chim. Acta 614 (2008) 1e26. polymer solar cells, J. Chin. Chem. Soc. 61 (2014) 115e126.
[4] J. Castrellon-Uribe, M.E. Nicho, G. Reyes-Merino, Remote optical detection of [21] H. Kim, S. Nam, J. Jeong, S. Lee, J. Seo, H. Han, Y. Kim, Organic solar cells based
low concentrations of aqueous ammonia employing conductive polymers of on conjugated polymers: history and recent advances, Korean J. Chem. Eng. 31
polyaniline, Sens. Actuators B Chem. 141 (2009) 40e44. (2014) 1095e1104.
[5] C. Della-Casa, A. Fraleoni-Morgera, M. Lanzi, P. Costa-Bizzarri, L. Paganin, [22] J. Maiti, B. Pokhrel, R. Boruah, S.K. Dolui, Polythiophene based fluorescence
F. Bertinelli, L. Schenetti, A. Mucci, M. Casalboni, F. Sarcinelli, A. Quatela, sensors for acids and metal ions, Sens. Actuators B 141 (2009) 447e451.
Preparation and characterization of thiophene copolymers with second order [23] Y. Liu, K. Ogawa, K.S. Schanze, Conjugated polyelectrolytes as fluorescent
non-linear optical properties, Eur. Polym. J. 41 (2005) 2360e2369. sensors, J. Photochem. Photobiol. C 10 (2009) 173e190.
[6] Z. Shi, X. Zhang, Z. Cui, Synthesis and characterization of thiophene-containing [24] V.C. Goncalves, D.T. Balogh, Optical chemical sensors using polythiophene
chromophores for nonlinear optical (NLO) materials, J. Nonlinear Opt. Phys. derivatives as active layer for detection of volatile organic compounds, Sens.
 J. Castrellon-Uribe et al. / Optical Materials 58 (2016) 93e101 101

Actuators B Chem. 162 (2012) 307e312. (2006) 276e285.

[25] C. Guo, S. Jiang, W. Zhu, X. Yang, M. Pei, G. Zhang, Polythiophene based [29] R. Nomura, K. Yamada, T. Masuda, A chromophore-labeled poly(N-
fluorescent probe for copper ions with high sensitivity, J. Appl. Polym. Sci. 132 propargylamide): a new strategy for a stimuli-responsive conjugated poly-
(2015) 42440. mer, Chem. Commun. 5 (2002) 478e479.
[26] J.A. Del-Oso, J.L. Maldonado, G. Ramos-Ortíz, M. Rodríguez, M. Güizado- [30] K.T. Grattan, Z.Y. Zhang, Fiber Optic Fluorescence Thermometry, Chapman and

rez-Gutie
Rodríguez, J. Escalante, B.A. Frontana-Uribe, E. Pe
rrez, R. Santillan, Hall, London, 1995.
New polythiophene derivatives and enhanced photovoltaic effect by a boron [31] H.D. Duong, J.I. Rhee, Exploitation of thermo-effect of rhodamine B entrapped
compound blended with them in OPVs cells, Synth. Met. 196 (2014) 83e91. in solegel matrix and silica gel for temperature detection, Sens. Actuators B
[27] J.R. Lakowicz, Principles of Fluorescence Spectroscopy, third ed., Springer, 124 (2007) 18e23.
New York, 2011. [32] S. Uchiyama, A. Prasanna de Silva, K. Iwai, Luminescent molecular ther-
[28] S. Khoee, H.R. Memarian, Fluorescence self-quenching of substituted N,a- mometers, J. Chem. Educ. 83 (2006) 720e727.
diphenylnitrones in various solvents, J. Photochem. Photobiol. A Chem. 177