Materials Science in Semiconductor Processing 61 (2017) 5056

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Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Electrospinning of P3HT-PEO-CdS bers by solution method and their MARK

properties

D. Hernndez-Martneza, M.E. Nichoa, , Hailin Hub, U. Len-Silvac, M.C. Arenas-Arrocenad,
C.H. Garca-Escobara
a
Centro de Investigacin en Ingeniera y Ciencias Aplicadas, Universidad Autnoma del Estado de Morelos. (UAEM), Av. Universidad 1001, Col. Chamilpa,
C.P. 62210 Cuernavaca, Morelos, Mxico
b
Instituto de Energas Renovables, Universidad Nacional Autnoma de Mxico, Priv. Xochicalco S/N, Temixco, Morelos 62580, Mxico
c
Instituto Nacional de Electricidad y Energas Limpias, Reforma 113, Temixco C.P. 62490, Morelos, Mxico
d
Escuela Nacional de Estudios Superiores, Unidad Len, Universidad Nacional Autnoma de Mxico, Boulevard UNAM No. 2011, Predio el Saucillo y el
Potrero, 36969 Len Guanajuato, Mxico

A R T I C L E I N F O A BS T RAC T

Keywords: Homogeneous composite bers of poly(3-hexylthiophene) (P3HT)-polyethylene oxide (PEO)-Cadmium Sulde

Fibers (CdS) were manufactured by electrospinning technique using chloroform as solvent. The incorporation of CdS
Electrospinning in the composite bers was determined by SEM, FTIR and TGA techniques. SEM and confocal microscopy have
Nanocomposites been used to determine size, surface morphology and distribution of the uorescence phase in the bers. A
Poly(3-hexylthiophene)
morphology change in P3HT/PEO bers was caused by the presence of CdS: porous morphology was obtained
CdS nanoparticles
for low CdS concentration (3.8 wt% and less) and when the content of CdS nanoparticles is higher, they were
concentrated at the center of the bers. The photoluminescence response was modied with CdS inside the
P3HT-PEO bers. By XRD it was determined that the introduction of CdS nanoparticles in the P3HT-PEO bers
caused disorder in P3HT chains. The obtained composite bers are promising materials for optic and electronic
applications.

1. Introduction properties and ease processability in solution [5]. After obtaining

The conductive polymers have attracted attention in the last
decades because of their potential applications as optic and electronic
materials. The development of simple and eective strategies to
manipulate the optical absorption (and emission) of conjugated
macromolecules by changing their molecular assembly and ordering
has signicant potential not only for gaining further understanding of
this interesting class of materials, but also for their wide spread
utilization in Plastic Electronic products [1]. The conjugated poly-
thiophenes are the most promising polymers due to their environ-
mental and thermal stability, low-cost synthesis and processability,
which may lead various applications such as materials for batteries and
solar energy conversion [2].
Sugimoto et al. [3], reported in 1986 a very simple method to
prepare poly(3-alkylthiophenes) (P3AT) by chemical oxidation method
of 3AT using FeCl3 as oxidant. The obtained products showed
molecular weight ranging from Mn=30k to 300k and polydispersity
ranging from 1.3 to 5 [4]. The poly(3-hexylthiophene) (P3HT) is one of
the most extensively studied P3AT due to its excellent electrical
P3HT, the route of processing can highly inuence the internal
structure of the polymer. Electrospinning process is one of the low-
cost and versatile methods that can produce polymer nanobers.
However, it is not possible achieve the electrospinning of a single
conjugated polymer because of the absence of chain entanglement in
that; macromolecules of P3HT only exhibit a rigid rod conformation in
a solution. The chain entanglement is a prerequisite for electrospinning
[6]. When P3HT is mixed with polymers such as poly(ethylene oxide)
(PEO), chain entanglement is induced to increase the viscosity and
spinnability [7].
Considering the possible application of optoelectronic devices,
nanoscale inorganic semiconductor llers have been incorporated into
the composite polymer solution for electrospinning. Park et al. [8]
prepared composite bers via chemical polymerization of pyrrole (Py)
on the surface of a commercial porous graphite ber matrix. Titania
nanobers obtained by electrospinning were covered by Poly(3,4-
ethylendioxythiophene): polystyrene sulfonate (PEDOT:PSS) and poly-
aniline: polystyrene (PANI:PS) by means of dip-coating [9,10].
Electrospun FeCl3/PS bers were covered by polypyrrole (PPy) [11].

Corresponding author.
E-mail address: menicho@uaem.mx (M.E. Nicho).

http://dx.doi.org/10.1016/j.mssp.2016.12.039
Received 28 July 2016; Received in revised form 5 November 2016; Accepted 31 December 2016
Available online 10 January 2017
1369-8001/ 2017 Elsevier Ltd. All rights reserved.
D. Hernndez-Martnez et al.
Carbon nanotubes (CNT)/PANI composites were prepared from the
CNT/aniline nanober oxidation, followed by the electrospinning
technique [12]. Salimbeygi G. et al. fabricated electrospun bers of
poly(vinyl alcohol) (PVA), polyaniline (PANI), and multi-wall carbon
nanotubes (MWCNTs) composite from solutions [13]. Conductive
nanobers of poly(vinylidene uoride) (PVDF) lled with polyaniline
(PANi)-coated MWCNTs were fabricated using PVDF solution with
PANI-coated MWCNTs in the electrospinning technique [14].
Poly(vinyl alcohol)-silver nanoparticles-poly(3, 4-ethylene dioxythio-
phene)/poly(styrene sulfonate) (PVA:AgNPs: PEDOT/ PSS) were gen-
erated as ultra-ne electrospun bers [15].
Regarding to the manufacture of composite polythiophenes/inor-
ganic bers, to our knowledge there are no additional reports to our
previous research work related to preparation and characterization of
P3HT- cadmium sulde (CdS) bers prepared by in-situ synthesis of
CdS in presence of P3HT bers, i.e., by precipitation of CdS on P3HT
washed bers [16]. In that paper, the eect of the concentration of the
precursor solutions on the precipitation of CdS on P3HT bers was
studied by choosing Cadmium Acetate of 3 or 5 mg with Na2S of 2.9 or
4.9 mg [16]. In this paper we present a new fabrication procedure to
produce P3HT-CdS composite bers by mixing P3HT, PEO and CdS in
a chloroform solution. The obtained bers were characterized by SEM,
confocal microscopy, FTIR, TGA, Photoluminescence and XRD, and
compared with those reported in our previous work [16]. We determine
that the new method allowed the incorporation of CdS particles inside
the bers, which signicantly inuenced on the properties of the bers,
as described in the result section.
2. Materials and methods
2.1. Synthesis of P3HT
P3HT was chemically synthesized at 0 C under inert atmosphere
using FeCl3 as an oxidant, the same procedure reported in our previous
work [16]. The nal P3HT product showed Mn=62,365 g/mol,
Mw=256,454 g/mol and PDI=4.1, estimated by GPC in THF using
polystyrene as standard. The same P3HT product also showed 88% of
HT dyads, which was determined by 1H NMR.
2.2. Synthesis of CdS
CdS was synthesized at room temperature using Na2S (Fermont)
and Cadmium Acetate (Cd (OOCCH3) 2 2H2O) (Alfa Aesar, 99.999%) as
precursors, according to Martnez-Alonso C. et al. [17]. In the reported
method, a 0.1 M solution of Na2S and 0.1 M solution of cadmium
acetate (Cd (OOCCH3)22H2O,) were prepared in methanol. The
solution temperature was 25 C (room temperature). The cadmium
ion solution was added slowly into the Na2S solution while stirring
constantly. The solution changed from transparent to yellow, indicating
that CdS was formed. The reaction time was 30 min. The CdS
precipitates were washed by centrifugation at 4400 rpm for 3 min, 3
times with 50 mL of deionized water and 2 subsequent times with
50 mL of methanol. The resulting CdS NPs were dried at 50 C for 48 h.
The obtained CdS product contained crystalline grains of size of about
3 nm, observed by TEM and showed an optical band-gap between 2.44
and 2.54 eV [17].
2.3. Preparation of P3HT-PEO bers by electrospinning
Electrospinning solution was prepared by dissolving rst P3HT
(80 wt%) and then PEO (20 wt%) (Mw=1,000,000, SigmaAldrich) in
chloroform solvent. The P3HT solution was stirred for 15 min, followed
by adding PEO into the solution, and the composite polymer solution
was stirred for 20 min until the solution was homogeneous. A syringe
was lled with the P3HT-PEO polymer solution and it was placed in an
injection pump (NEW ERA NE-300 model) connected to a voltage
51
Materials Science in Semiconductor Processing 61 (2017) 5056
source (CZE1000R Spellman). The electrospinning parameters were
set as: solute concentration (P3HT-PEO in solvent)=2.8 wt%, applied
voltage=11 kV, ow rate=3.2 mL/h, and distance from the needle tip to
the collector=24 cm. The bers were deposited on an aluminum
collector plate of 25 cm2.
2.4. Synthesis of P3HT-PEO-CdS bers (solution method)
CdS nanoparticles were added to the previous P3HT-PEO polymer
solution. To see the eect of the CdS concentration in the P3HT/PEO
bers, 3 dierent CdS concentrations were tested for obtaining P3HT-
PEO-CdS bers (1.3, 3.8 and 6.3 wt% of CdS in P3HT-PEO). CdS
powder was previously subjected to ultrasound for 30 min to pulverize
all the CdS nanoparticles clusters, obtaining a very ne powder. Then
chloroform solvent was added into that CdS ne powder to disperse it
again for 30 min with ultrasound and a much better dispersion of CdS
nanoparticles in the solvent was achieved; CdS nanoparticles were
suspended in the solvent. When the dispersion is homogeneous, the
P3HT-PEO solution, previously with stirring during 30 min, was added
to the CdS suspension and stirred by 5 h. After that the mixture
solution was electrospunned using the following parameters: applied
voltage=11 kV, ow rate=3.2 mL/h, Distance from needle tip to
collector=24 cm.
2.5. Characterization
Morphology and elemental content of CdS and P3HT-PEO and
P3HT-PEO-CdS bers were characterized by SEM (Hitachi SE-SEM
5500) equipped with an EDX analysis system. To determine the
morphology of CdS nanoparticles by SEM, they were sonicated by
40 min, subsequently sonicated again in ethanol solvent by 20 min. A
drop of that solution was deposited onto an aluminum substrate and
heated to 80 C and then SEM images were taken. The uorescence
confocal microscope (Zeiss Axiovert 200 LSM 510, HeNe Laser
excitation of 633 nm, 10% power) was used to determine the uores-
cence phase on the ber surface. Fourier Transform Infrared
Spectroscopy (FTIR): Attenuated Total Reection (ATR) spectra of
ber samples were recorded in a FT-IR Spectrometer Frontier MIR
(Perkin Elmer). Thermal stability and decomposition temperature of
the bers were determined by Thermogravimetric Analysis (TGA-TA
Q500 equipment); the samples were heated at 10 C/min rate under
nitrogen atmosphere. X-ray diraction (XRD) patterns were recorded
in a Rigaku Ultima IV X-ray diractometer (CuK-radiation;
=0.154 nm), with a scanning rate of 1/min from 10 to 40 in 2
range (Mode: Parallel beam and grazing angle: 1). For XRD measure-
ment P3HT was deposited on Corning glass. Finally, photolumines-
cence characterization of the bers was performed in a uorospect-
rometer (LAMBDA 650, Perkin Elmer) at excitation wavelengths of
450 nm.
3. Results and discussion
3.1. Morphology of CdS and P3HT-PEO-CdS bers
SEM images of CdS nanoparticles are shown in Fig. 1. They have an
agglomerated granular morphology with an average diameter lower
than 10 nm.
SEM images of the P3HT-PEO-CdS bers with dierent CdS
content are shown in Fig. 2. They showed a dependence of the
morphology on the CdS content. The bers with 1.3 wt% of CdS
showed a rough and porous surface morphology (Fig. 2a). In the inset
of Fig. 2a, the porosity could be well appreciated. When we compared
this image with that of P3HT-PEO bers without CdS nanoparticles,
obtained in our previous work (Fig. 1b of Ref [16]), the present sample
exhibited a higher porosity. EDX analysis (Table 1) proved the
presence of CdS inside the bers. The porosity over the entire bers
D. Hernndez-Martnez et al. Materials Science in Semiconductor Processing 61 (2017) 5056

Fig. 1. SEM images of CdS nanoparticles at the magnication of (a) 200 KX and (b) 450 KX.

probably indicates the incorporation of CdS nanoparticles throughout Table 1

the volume of the P3HT-PEO bers. When the concentration of CdS S/Cd atomic ratio in P3HT-PEO-CdS fibers with different CdS content obtained by EDX
technique.
was increased to 3.8 wt% (Fig. 2b), P3HT-PEO-CdS bers showed even
a higher porosity and rugosity (inset of Fig. 2b) than in the above Sample S/Cd atomic ratio
mentioned case. The increased porosity is probably due to higher
content of CdS incorporated in the volume of the bers. EDX analysis P3HT-PEO-CdS(1.3 wt%) 1211.80
(Table 1) of the sample also indicated the presence of CdS in the bers, P3HT-PEO-CdS(3.8 wt%) 68.44
P3HT-PEO-CdS(6.3 wt%) 3.55
showing a higher CdS content than the rst sample.
To estimate the porosity of the composite bers, an image processor
software (image J) was used to count the sizes of the pores and the formation of holes at the surface of the bers (Fig. 2c), and, at the same
results were showed in Fig. 3. It was clear that the average pore size time, CdS agglomeration was observed inside the bers. It seems that
was about 0.3 m for the sample of 1.3 wt% of CdS and 0.4 m for the the polymers were concentrated at the surface of the bers by forming a
sample of 3.8 wt% of CdS. lm with holes lled with the CdS clusters (inset of Fig. 2c) and the
In the case of 6.3 wt% of CdS, the P3HT-PEO-CdS bers showed the

Fig. 2. SEM images of P3HTPEO-CdS bers: (a) 1.3 wt% of CdS, (b) 3.8 wt% of CdS and (c) 6.3 wt% of CdS.

52
D. Hernndez-Martnez et al.
Fig. 3. Pore distribution for SEM images of P3HTPEO-CdS bers: (a) 1.3 wt% of CdS and (b) 3.8 wt% of CdS.
distribution of hole size in the polymeric lm was inhomogeneous. As
expected, EDX analysis reected a higher content of Cd by increasing
the weight percentage of CdS in the composite bers (Table 1).
The observed results could be explained as follow: CdS nanoparti-
cles (clusters of dierent size) are incorporated between the polymer
chains. Inside the bers, parts of the polymer chains interact with CdS
clusters and parts of them do not. The latter ones are those that
generate the porosity, mainly around of CdS clusters. When the CdS
concentration is higher (3.8 wt% of CdS), the number and size of CdS
clusters increase and so the porosity of the composite bers. To
continue increasing the CdS concentration up to 6.3 wt%, the CdS
clusters are so large that they are separated from the polymer chains
and concentrated at the center of the bers.
To further conrm the distribution of dierent phases inside the
composite bers, Fig. 4 shows uorescence images of two P3HT-PEO-
CdS bers: 3.8 wt% of CdS (Fig. 4a) and 6.3 wt% of CdS (Fig. 4b). PEO
is not uorescent, neither CdS emits light under the excitation by the
light of 633 nm (1.95 eV) wavelength, whose energy is smaller than the
band gap of CdS (about 2.42 eV). Therefore, the only phase that could
give a signal to band emission is the P3HT phase in the composite
bers, whose band gap is about 1.9 eV. The composite bers with less
amount of CdS (Fig. 4a) showed a lower uorescence intensity at the
surface of the bers. It suggests that less content of P3HT, or larger
percentage of PEO or CdS appeared at that surface, which conrms the
observation in the SEM images of the same samples (Fig. 2b and c). As
the content of CdS nanoparticles increased in the composite bers, they
started to gather inside the bers, pushing the polymers onto the ber
surface and the uorescent phase (P3HT) was much more appreciated,
as can be seen in Fig. 4b. It concludes that a small percentage of CdS
Fig. 4. Confocal microscopy images of P3HT-PEO-CdS bers with dierent CdS concentration: a) 3.8 wt% of CdS, and b) 6.3 wt% of CdS.
53
Materials Science in Semiconductor Processing 61 (2017) 5056
seems to be homogeneously distributed through all the volume of the
composite bers, but a larger one induces the CdS cluster formation
inside the bers.
3.2. FTIR study of P3HT-PEO-CdS bers
Fig. 5 shows the FTIR spectra of P3HT, PEO, and P3HT-PEO-CdS
bers (1.3, 3.8 and 6.3 wt% de CdS), giving the characteristic bands of
P3HT (722, 820, 1114, 1377, 1460, 1510, 2852, 2920, 2954 cm1) and
PEO (841, 945, 1093, 1278, 1342, 1460 cm1) [16]. Although the
stretching band of CdS cannot be observed by FT-IR spectra, higher
content of CdS (3.8% and 6.3%) indeed increased the P3HT absorption
band at 820 cm1 in the composite bers. Since these FT-IR spectra
were recorded in an ATR mode, surface molecules of the test samples
contributed in the spectra. In ATR mode the penetration depth into the
sample is typically between 0.5 and 2 m, with the exact value being
determined by the wavelength of light, the angle of incidence and the
indices of refraction for the ATR crystal and the medium being probed.
It is to say that the composite bers with a larger percentage of CdS
have more P3HT molecules at the surface, the same conclusion from
SEM and uorescent images in Figs. 2 and 4, respectively.
3.3. Thermal characterization of P3HT, PEO and P3HT-PEO-CdS
bers
Fig. 6 shows the TGA curves of P3HT, PEO, P3HT-PEO and P3HT-
PEO-CdS bers. The maximum decomposition temperatures of PEO
and P3HT were 391 C and 494 C, respectively. The P3HT-PEO bers
showed two decomposition temperatures at 402 and 479 C, assigned
D. Hernndez-Martnez et al. Materials Science in Semiconductor Processing 61 (2017) 5056

P3HT-PEO-CdS ( 6.3 wt%)

820 P3HT
80 670 nm (1.85 eV)

P3HT-PEO
P3HT-PEO-CdS (1.3 wt%)
Transmittance (a.u)

60

INTENSITY (a.u)
P3HT-PEO-CdS (3.8 wt%)
P3HT-PEO-CdS ( 3.8 wt%)
P3HT-PEO-CdS (6.3 wt%) P3HT FILM 674 nm (1.84 eV)
40 639 nm
PEO (1.94 eV)

20 526 nm 600 nm
960 840 (2.36 eV) (2.07 eV)
1092
P3HT-PEO
0 663 nm (1.87 eV)
1400 1200 1000 800 600 500 550 600 650 700 750
Wavenumber (cm-1) WAVELENGHT (nm)

Fig. 5. FTIR spectra in the range of 5001200 cm1 of P3HT-PEO-CdS bers with
dierent concentrations of CdS. Individual PEO and P3HT spectra were added for
comparison.
to decomposition of PEO and P3HT, respectively. The P3HT-PEO-CdS
bers showed also two decomposition temperatures but at lower
temperatures: 390 and 475 C for bers with 1.3 wt% of CdS, 394
and 476 C for bers with 3.8 wt% of CdS, and 393 and 471 C for
bers with 6.3 wt% of CdS. This indicates that the composite bers
were formed by separated components, P3HT, PEO and CdS, and the
mixture is only physical. The same phenomenon was observed in the
case of P3HT bers coated with CdS nanoparticles (in-situ method)
[16].
3.4. Photoluminescence analysis
Photoluminescence (PL) can measure the energy gap and the
impurities in a material [18]. Fig. 7 shows the PL spectra of P3HT
lm, P3HT-PEO bers and P3HT-PEO-CdS bers, under excitation of
450 nm. P3HT lm showed an energy gap of 1.94 eV. However, in
P3HT-PEO bers the energy gap was decreased to 1.87 eV. Similar
results were found by Hellmann et al. [19]; they recorded dierent PL
spectra for neat P3HT and P3HT-PEO blend lms and founded that the
minimum energy required to excite the P3HT-PEO blend lm was
lowered compared to the neat P3HT lm by approximately ~0.06 eV
(from ~2 eV for the neat lm to ~1.94 eV for the blends). Kim et al.
[20] also observed that the spectrum of the electrospun nanobers
(P3HT-PEO) is red-shifted by 1520 nm with respect to that of the
P3HT lm. Therefore, the presence of PEO in P3HT, regardless if it is
lm or ber, reduced the energy band gap of the composite P3HT-PEO
material. Hellmann et al. [19] showed that this red-shift is very likely
due to the planarization of the conjugated polymers backbone in the
presence of PEO. According to Jiang et al. [21], strong interchain
Fig. 7. Photoluminescence spectra at 450 nm for: P3HT lm, P3HT/PEO and P3HT-
PEO-CdS bers.
interaction in regioregular (RR) P3HT is already evidenced by the
usually weaker photoluminescence of RR-P3HT than that of regioran-
dom (rra)-P3HT. Thus in our case, P3HT chains probably had a higher
order with the presence of PEO inside the bers, which is corroborated
later in X-ray analysis. The fact that electrospinning induces a lower
energy gap of P3HT bers suggests that the P3HT polymer chains
should be extended along the applied electric eld, leading to a red-
shifted absorption spectrum [20].
The P3HT-PEO-CdS bers with 3.8 wt% of CdS showed a similar
emission band to that of P3HT/PEO bers but with the increase of
band intensity and a furthermore red-shift (0.03 eV). Most interest-
ingly, when the CdS content was increased to 6.3 wt%, the intensity of
the band at about 1.85 eV was largely increased. The increased
intensity with the CdS content in the region of 1.841.85 eV is due
to a large amount of P3HT at the surface of the composite bers, as
noted in the confocal images. Additionally, the CdS content in the
solution probably causes a disorder of P3HT chains within the bers,
and this was reected also by an increment in the PL [21; an increase of
CdS content caused a larger disorder in the polymer chains and
consequently a further increase in the intensity of the uorescent
signal.
Finally, the small emission bands at 2.07 and 2.36 eV appeared in
the composite P3HT-PEO bers. They probably were due to a low
percentage of P3HT chains more jumbled introduced by the molecules
of PEO. With the addition of CdS in the composite bers, their relative
intensity was reduced.
3.5. X-ray analysis
The XRD results conrmed that P3HT chains had a higher order

a) b) 14 479 C
100
12 PEO
P3HT 471 C
80
10 P3HT-PEO
DERIVATIVE

P3HT-PEO-CdS(1.3 % wt) 473 C

% WEIGHT

P3HT-PEO-CdS(3.8 % wt)
60 8 P3HT-PEO-CdS(6.3 % wt)

40 PEO 6 393 C
P3HT 385 C
P3HT-PEO 402 C
P3HT-PEO-CdS(1.3 % wt)
4
20
P3HT-PEO-CdS(3.8 % wt)
391 C
P3HT-PEO-CdS(6.3 % wt) 2
0
476 C 494 C
0
100 200 300 400 500 600 700 100 200 300 400 500 600 700
TEMPERATURE (C) TEMPERATURE (C)
Fig. 6. TGA analysis of P3HT-PEO-CdS bers, P3HT lm and PEO power: a) weight percentage vs. temperature and b) derivatives vs. temperature.

54
D. Hernndez-Martnez et al. Materials Science in Semiconductor Processing 61 (2017) 5056

0 10 20 30 40 50 60 70 Ref. [16]), wherein CdS was deposited only at the surface of the bers.
3000
e) P3HT-PEO-CdS (6.3 % wt) The electrospun composite P3HT-PEO-CdS bers could have interest-
2000 ing applications, either in sensors or optoelectronic devices, which
require exible photoluminescent self-standing materials.
1000
4. Conclusions
5000
0
4000
d) P3HT-PEO-CdS (3.8 % wt)
Composite P3HT-PEO-CdS bers were obtained by electrospinning
3000
using solution method. This method, compared with the previous
2000
reported method (in-situ synthesis of CdS in presence of P3HT bers),
1000
allowed a good dispersion of CdS inside the bers when the percentage
Intensity (cps)

400
0
CdS (00-002-0563) P3HT-PEO-CdS (1.3 % wt)
300 c)
200
100
400
0 the CdS content. A larger order of the P3HT polymer chains was given
b) P3HT-PEO
300
PEO (00-057-1528)
200
100
400
0 Acknowledgements
P3HT FILM
300
a) P3HT (00-054-2080)
200
100
0 C. Martnez-Alonso for her guidance in the synthesis of CdS nanopar-
0 10 20 30 40 50 60
2-Theta (deg)
Fig. 8. X-ray diraction patterns of: a) P3HT lm with card of P3HT of orthorhombic
crystal system (00-054-2080), b) P3HT-PEO bers with card of PEO for monoclinic
crystal system (00-057-1528), c) P3HT-PEO-CdS bers with 1.3%wt of CdS with card of
CdS for Greenockite, CdS (00-002-0563), d) P3HT-PEO-CdS bers with 3.8%wt of CdS,
and e) P3HT-PEO-CdS bers with 6.3%wt of CdS.
with the presence of PEO into the bers (Fig. 8). In the case of P3HT
lm, a well-dened diraction peak with the maximum intensity at
2=5.3 was observed, together with a wide peak at 2 between 13
and 37. The peaks at 2=5.3, 19.08, 24.3 and 26.3 correspond to
the Miller indices (1 0 0), (2 1 1), (4 1 0) and (1 2 1), respectively,
identied with the card of P3HT: 00-054-2080 (the crystal system:
Orthorhombic). For P3HT-PEO bers, additional peaks at 2 =5.3
appeared in the X-ray diraction pattern (2=19.08, 23.3, shoulders
at 24.3, 26.3, 26.9, 27.8 and 32.3). The peaks at 2=19.08, 23.3,
26.9, 27.8 and 32.3 correspond to the Miller indices (1 2 0), (1 1 2),
(1 3 1), (0 4 1) and (0 2 5), respectively, identied with the card of PEO
Diraction; 00-057-1528 (the crystal system: monoclinic). Thus the
peak at 23.3 with a shoulder at 24.3 correspond to the superposition
of two Miller indices, (1 1 2) of PEO and (4 1 0) of P3HT. Finally, the
peak at 19.08 probably is the superposition of two Miller indices, (1 2
0) of PEO and (2 1 1) of P3HT.
The presence of CdS in the P3HT-PEO-CdS bers was corroborated
by the appearance of the peak at 26.96 and the shoulder at 43.9,
corresponding to the Miller indices (0 0 2) and (1 1 0), respectively, of
CdS crystalline phase (Greenockite, diraction card: 00-002-0563; the
crystal system: hexagonal). As the amount of CdS in the composite
bers increased, the intensity of both P3HT crystalline phase (dirac-
tion peak at 5) and PEO one (diraction peak at 19.08) is notably
increased (see the unit of intensity in Fig. 8), and the presence of CdS
can be observed as a shoulder at 26.96. XRD analysis conrmed that
the CdS content in the P3HT-PEO bers caused a ordering of P3HT
chains within the composite bers.
Finally, the advantage of this ber preparation method, by incor-
porating CdS into the solution before the electrospinning process, is
that the CdS nanoparticles could be incorporated in the volume of the
bers, unlike the in-situ method shown in the previous work (Fig. 4 of
of CdS is low (3.8 wt% and less), and the porosity of the bers
increased with the CdS concentration. When the CdS concentration is
larger than 6 wt%, clusters of CdS are formed inside the bers and
covered by the composite polymer P3HT-PEO. Photoluminescence
intensity of P3HT/PEO/CdS bers was increased and red-shifted with
with the presence of CdS into P3HT-PEO bers, together with the
reduced band gap. Porous exible photoluminescent P3HT-PEO-CdS
bers are promising materials for optoelectronic applications.
The authors acknowledge to the FONDO SECTORIAL CONACYT-
SENER-SUSTENTABILIDAD ENERGTICA through the CEMIE-Sol/
27 (project no. 207450). for nancial support. The authors thank to Dr.
70
ticles, Dr. Patricia Altuzar Coello for TGA and XRD characterization,
Ing. Rogelio Morn Elvira for SEM images, Dr. Gregorio Cadenas for
1H NMR and GPC characterization, and Elsa Nydia Hernndez Ros for
confocal microscope characterization.
References
[1] C. Hellmann, F. Paquin, N.D. Treat, A. Bruno, L.X. Reynolds, S.A Haque,
P.N. Stavrinou, C. Silva, N. Stingelin, Controlling the interaction of light with
polymer semiconductors, Adv. Mater. 25 (2013) 49064911.
[2] W.J. Feast, J. Tsibouklis, K.L. Pouwer, L. Groenendaal, E.W. Meijer, Synthesis,
processing and material properties of conjugated polymers, Polymer 37 (1996)
50175047.
[3] R. Sugimoto, S. Takeda, H.B. Gu, K. Yoshino, Preparation of soluble polythiophene
derivatives utilizing transition metal halides as catalysts and their property, Chem.
Express 1 (1986) 635638.
[4] M. Pomerantz, J.J. Tseng, H. Zhu, S.J. Sproull, J.R. Reynolds, R. Uitz, H.J. Arnott,
M.I. Haider, Processable polymers and copolymers of 3-alkylthiophenes and their
blends, Synth. Met. 41 (1991) 825830.
[5] K.H.K. Chan, T. Yamao, M. Kotaki, S. Hotta, Unique structural features and
electrical properties of electrospun conjugated polymer poly(3- hexylthiophene)
(P3HT) bers, Synth. Met. 160 (2010) 25872595.
[6] S. Sundarrajan, R. Murugan, A.S. Nair, S. Ramakrishna, Fabrication of P3HT/
PCBM solar cloth by electrospinning technique, Mater. Lett. 64 (2010) 23692372.
[7] I.D. Norris, M.M. Shaker, F.K. Ko, A.G. MacDiarmid, Synth. Met 114 (2000)
109114.
[8] J.H. Park, J.M. Ko, O.O. Park, D.-W. Kim, Capacitance properties of graphite/
polypyrrole composite electrode prepared by chemical polymerization of pyrrole on
graphite ber, J. Power Sources 105 (2002) 2025.
[9] E. Zampetti, A. Macagnano, S. Pantalei, A. Bearzotti, PEDOT: PSScoated titania
nanobers for NO2 detection: study of humidity eects, Sens. Actuators, B Chem.
179 (2013) 6973.
[10] E. Zampetti, S. Pantalei, A. Bearzotti, C. Bongiorno, A. Macagnano, TiO2 nano-
brous chemoresistors coated with PEDOT and PANi blends for high performance
gas sensors, Procedia Eng. 47 (2012) 937940.
[11] J.Wang, H.E.Naguib, A.Bazylak, Electrospun porous conductive polymer mem-
branes, in: Proceedings of SPIE, vol. 8342 83420F-1
[12] J. Qi, F. Guanggang, X. Deyu, J. Shengqiang, C. Zhiliang, H. Bin, Z. Yong,
Preparation of carbon nanotube/polyaniline nanober by electrospinning, Procedia
Eng. 27 (2012) 7276.
[13] S. Golestan, N. Komeil, M.S. Ahmad, M. Reza, M. Firoozmehr, Microwave
absorption properties of polyaniline/poly(vinyl alcohol)/multi-walled carbon na-
notube composites in thin lm and nanober layer structures, Macromol. Res. 23
(2015) 741748.
[14] A. Sarvi, A.B. Silva, R.E.S. Bretas, U. Sundararaj, A new approach for conductive
network formation in electrospun poly(vinylidene uoride) nanobers, Polym., Int.
64 (2015) 12621267.
[15] P. Pisesweerayos, S. Dangtip, P. Supaphol, T. Srikhirin, Conductive nanocomposite

55
D. Hernndez-Martnez et al.
aligned bers of PVA-AgNPs-PEDOT/PSS, Adv. Mat. Res. 1033 (2014) 10091019.
[16] D. Hernndez-Martnez, C. Martnez-Alonso, M.M. Castillo-Ortega, M.C. Arenas-
Arrocena, M.E. Nicho, Preparation and characterization of electrospun bers
containing poly(3-hexylthiophene) and poly(3-hexylthiophene)/CdS, Synth. Met.
209 (2015) 496501.
[17] C. Martnez-Alonso, H.J. Cortina-Marrero, C.S. Coria-Monroy, M.C. Arenas,
M.E. Nicho, H. Hu, Solution synthesized CdS nanoparticles for hybrid solar cell
applications, J. Mater. Sci: Mater. Electron 26 (2015) 55395545.
[18] P.Y. Yu, M. Cardona, Fundamentals of Semiconductors, Physics and Materials
Properties, 4 ed., Springer, New York, 2010.
56
Materials Science in Semiconductor Processing 61 (2017) 5056
[19] C. Hellmann, F. Paquin, N.D. Treat, A. Bruno, L.X. Reynolds, S.A. Haque,
P.N. Stavrinou, C. Silva, N. Stingelin, Controlling the interaction of light with
polymer semiconductors, Adv. Mater. 25 (2013) 49064911.
[20] T. Kim, J.H. Im, H.S. Choi, S.J. Yang, S.W. Kim, C.R. Park, Preparation and
photoluminescence (PL) performance of a nanoweb of P3HT nanobers with
diameters below 100 nm, J. Mater. Chem. 21 (2011) 1423114239.
[21] X.M. Jiang, R. sterbacka, O. Korovyanko, C.P. An, B. Horovitz, R.A.J. Janssen,
Z.V. Vardeny, Spectroscopic studies of photoexcitations in regioregular and
regiorandom polythiophene lms, Adv. Funct. Mater. 12 (2002) 587597.