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Department of Materials Engineering, Ming Chi University of Technology, 84 Gunjuan Rd., Taishan Dist., New Taipei City 24301, Taiwan
Center for Thin Film Technologies and Applications, Ming Chi University of Technology, 84 Gunjuan Rd., Taishan Dist., New Taipei City 24301, Taiwan
Battery Research Center of Green Energy, Ming Chi University of Technology, 84 Gunjuan Rd., Taishan Dist., New Taipei City 24301, Taiwan
a r t i c l e
i n f o
a b s t r a c t
In this study, monodispersed colloidal titanium dioxide (TiO2) was synthesized and applied with
poly(3-octylthiophene-2,5-diyl) (P3OT), phenyl-C61-butyric acid methyl ester (PCBM), poly(3,4-ethylene
dioxythiophene) (PEDOT), and poly(styrenesulfonate (PSS) to fabricate an aluminum/calcium/P3OT:PCBM:
TiO2/PEDOT:PSS/indium tin oxide hybrid solar cell using spin coating and evaporation deposition. The effects
of the TiO2 content and annealing temperature on cell performances were investigated. The results showed
that optimization of the TiO2 content (15 wt.%) and annealing temperature (150 C) effectively enhanced the
performance of the hybrid solar cells. The PCBM and TiO2 absorbed more light photons in the P3OT:PCBM:
TiO2 active layer. The charge transfer in the P3OT:PCBM:TiO2 active layer was more efcient, increasing the
amount of photoluminescence quenching. The increased active layer surface roughness reduced the chargetransport distance and enhanced the internal light scattering and light absorption. The best values for the
open circuit voltage, short-circuit current density, ll factor, and efciency for the prepared hybrid solar cell
were 0.61 V, 9.50 mA/cm2, 34.46%, and 2.09%, respectively.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Organic photovoltaic solar cell technology based on conjugated
polymerfullerene composites is attractive because of its light weight,
mechanical exibility, and low production costs. High-efciency polymer solar cells are of interest as a potential source of renewable alternative electrical energy [14]. However, the low efciency of these
polymer solar cells limits their feasibility for commercial use. One of
the most promising methods for enhancing device efciency is to construct an interpenetrating network of electron-accepting (i.e., acceptor)
and -donating (i.e., donor) components in the active layers of solar cells.
To date, various hybrid solar cells have been reported using different
-conjugated polymers [511] and metal or metal oxides [1216].
Poly(3-octylthiophene) (P3OT) has a polar backbone (i.e., thiophene
ring) and nonpolar side chain (i.e., octal group) that are soluble in polar
and nonpolar solvents, providing a more exible choice of either polar
or nonpolar matrix polymers [1720]. The P3OT/semiconductor junction
produces a photovoltaic device that has physical characteristics that
strongly depend on the electronic and optical properties of P3OT and
the semiconductors that are used [21,22]. The P3OT/semiconductor junction may be described as a hybrid heterojunction barrier type, where
P3OT, in its highly doped state, behaves like a metal and the photocarriers
are generated in the semiconductor.
Corresponding author at: Department of Materials Engineering, Ming Chi University
of Technology, 84 Gunjuan Rd., Taishan Dist., New Taipei City 24301, Taiwan. Tel.: +886 2
29089899 4676; fax: +886 2 29084091.
E-mail address: yyyu@mail.mcut.edu.tw (Y.-Y. Yu).
0040-6090/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tsf.2013.03.084
Y.-Y. Yu, C.-Y. Ciou / Thin Solid Films 544 (2013) 318323
319
2.1. Materials
2.4. Characterization
The 3-octylthiophene, 1,3-bis(diphenylphosphino)proane] nickel (II) chloride (Ni(dppp)Cl2), tert-butylmagnesium chloride, and
tetrahydrofuran (THF, 99%) were obtained from Aldrich. Nbromosuccinimide (99%) was obtained from Acros. Hexane (95%)
and methanol (MeOH, 98%) were obtained from TEDIA (Faireld,
USA). Chlorobenzene anhydrous was obtained from Aldrich. The 6,6phenyl-C61-butyric acid methyl ester (PCBM) powder was obtained
from Uni-region (USA). All monomers were purchased and used without
purication.
2.2. Preparation of P3OT:PCBM:TiO2 (POPT) nanocomposites
First, the TiO2 NPs solution was prepared using the solgel procedure. The prepared TiO 2 NPs have an almost spherical shape with
a size around 20 nm. The detailed description could be found in our
previous study [27,28]. Then, P3OT was obtained by direct oxidation of
respective monomer using FeCl3 as the oxidant/catalyst at room temperature in an inert atmosphere [17]. Anhydrous FeCl3 (0.03835 mol)
dissolved in anhydrous CHCl3 was slowly added to 0.0254 mol of distilled monomer dissolved also in anhydrous CHCl3. The reaction
mixture was stirred at room temperature for 25 h. The product was precipitated in methanol, ltered and carefully washed with methanol,
hydrochloric acid, distilled water and acetone. The nal black P3OT
product was then dried at 55 C. Finally it was extracted in chloroform
to remove the insoluble part of the polymer. In a typical preparation,
0.0236 g of P3OT was added into 6 mL of chloroform, followed by the
addition of 0.051 g of PCBM. Next, the desired amount of the TiO2 colloidal solution was added into the P3OT:PCBM solution and stirred for
48 h to obtain the P3OT:PCBM:TiO2 nanocomposite solution. The solution was coated on the surface of the ITO glass substrate using spin coating at 3000 rpm for 20 s. The as-prepared lm was baked for 20 min at
150 C, 30 min at 200 C, and 60 min at 250 C, respectively. The product was labeled POPTX (X: a number representing the wt.% of TiO2 in
the nanocomposites).
2.3. Preparation of Al/Ca/P3OT:PCBM:TiO2/PEDOT:PSS/ITO hybrid solar
cell
Highly conducting polymer PEDOT/PSS was prepared from the
mixed solution of 3,4-ethylenedioxythiophene, 6 wt.% PSS, Na2S2O8,
and water at room temperature under stirring. Then, Fe2(SO4)3 was
added into the solution to extract the PEDOT/PSS. After 24 h, blue
black pure PEDOT/PSS was obtained by the ion-exchange reaction [29]. The hybrid solar cell devices were fabricated by spin coating. The polymer solar cells were prepared based on the following
procedure. The patterned ITO glass substrate was rst cleaned with
acetone and IPA ultrasonically, and was subsequently dried by N2
purging after being rinsed with DI water. The PEDOT/PSS was mixed
TiO2
(wt.%)
VOC
(V)
JSC
(mA/cm2)
FF
(%)
(%)
POPT0
POPT10
POPT15
POPT20
POPT25
0
10
15
20
25
0.57
0.58
0.61
0.60
0.59
0.21
1.04
9.50
6.72
3.12
28.09
29.41
34.46
31.99
32.42
0.03
0.18
2.09
1.31
0.60
320
Y.-Y. Yu, C.-Y. Ciou / Thin Solid Films 544 (2013) 318323
radiation = 1.54056 between 20 and 60 (2). The operation voltage and anode current were 40 kV and 30 mA, respectively.
(a)
Absorbance (arb. units)
0.4
POPT15
POPT20
0.2
POPT25
POPT10
POPT0
0.0
400
500
600
700
800
900
Wavelength (nm)
(b)
1.6x107
Intensity (arb.units)
POPT0
1.2x107
POPT10
8.0x106
POPT25
POPT20
4.0x106
POPT15
0.0
500
600
700
800
Wavelength (nm)
Fig. 2. (a) UVvis and (b) PL spectra of pristine P3OT:PCBM (POPT0) and P3OT:PCBM:
TiO2 (POPT) hybrid lms obtained at different TiO2 contents (1025 wt.%).
shown in Fig. 2(a). This shows that P3OT has a maximum absorption
peak at 525 nm. The absorbance at 525 nm increases with the TiO2
content. The P3OT molecules have a more regular arrangement
under the existence of TiO2 NPs, and thus, absorb more light and produce more electron-hole pairs in the active layer. However, decreased
absorbance was observed when the TiO2 content was higher than
20 wt.%. The maximum absorbance was obtained when the TiO2 content in P3OT:PCBM was 15 wt.%. Conversely, PL spectra show that the
maximum emissive peak was at 580 nm, as shown in Fig. 2(b). The
intensity of the emission decreased when the TiO2 NPs were added
to the active layer. The minimum emission occurred when the TiO2
content in the P3OT:PCBM was 15 wt.%. The results indicate that
adding TiO2 can enhance exciton dissociation at the P3OTTiO2 interface because of the production of potential energy gaps between the
P3OT and TiO2. The decreased PL emissive intensity conrms the
mentioned results.
Fig. 3 shows the IPCE spectra of the pristine P3OT:PCBM (POPT0)
and P3OT:PCBM:TiO2 (POPT) hybrid lms obtained at different TiO2
contents (i.e., 1025 wt.%). This shows that adding TiO2 NPs in
P3OT:PCBM can increase the value of IPCE from approximately 11%
to 60% (at 500 nm). Fig. 4 shows the JV curve of the ITO/PEDOT:
PSS/POPT/Ca/Al hybrid solar cell obtained in the dark and when illuminated. Fig. 4(a) shows that the addition of TiO2 NPs caused an increase in the leakage current density of the hybrid solar cells. In
addition, the components of the series resistance increased under
the existence of the TiO2 NPs. Conversely, Fig. 4(b) shows that the
prepared hybrid solar cell had an open circuit voltage (VOC) of 0.47
0.61 V. The value of VOC typically depends on the highest occupied
Y.-Y. Yu, C.-Y. Ciou / Thin Solid Films 544 (2013) 318323
70
60
POPT15
IPCE (%)
50
POPT20
40
POPT10
30
POPT25
POPT0
20
10
0
400
500
600
700
800
Wavelength (nm)
Fig. 3. IPCE spectra of pristine P3OT:PCBM (POCT0) and P3OT:PCBM:TiO2 (POPT) hybrid lms obtained at different TiO2 contents (1025 wt.%).
(a)
100
10
1
0.1
0.01
1E-3
POPT 0
POPT 10
POPT 15
POPT 20
POPT 25
1E-4
1E-5
1E-6
1E-7
1E-8
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
Voltage (V)
(b)
321
of the VOC, short-circuit current density (JSC), ll factor (FF), and efciency () of the hybrid solar cell with the P3HT:PCBM:TiO2 active layer
obtained at annealing temperature 150 C for 20 min are listed in
Table 1. As shown in Table 1, the best parameters obtained from cell
Al/Ca/PEDOT:PSS/POPT15/ITO was VOC = 0.61 V, JSC = 9.50 mA/cm2,
FF = 34.46%, and = 2.09%. These results show that the optimum
content of TiO2 NPs can effectively enhance the performance of hybrid
solar cells. The TiO2 NPs were randomly distributed in the polymer matrix, forming an interconnected network structure. The homogeneous
distribution was advantageous for both electron and hole carrier transport. However, when the TiO2 content was higher than the optimum
value, the performance of the cells began to decrease because the aggregation of TiO2 NPs hindered the continuous pathways for the charge
carriers [34]. Fig. 5 shows the AC impedance analysis of the hybrid
solar cell with POPT15 active layers obtained at various annealing
temperatures (110 C200 C) under AM1.5 illumination (100 mW/
cm2). Semicircles can help investigate the internal resistance of hybrid
solar cells [22,27]. The diagram clearly shows that the semicircle
diameter of the cells prepared at 150 and 170 C was much less than
those obtained at 110 C, 130 C, and 200 C. This result indicates that
annealing at an optimum temperature can effectively reduce cell resistance and enhance cell performance. Fig. 6 shows the TGA and DSC curves
of the P3OT, indicating that the thermal decomposition (Td) and melting
point (Tm) of the P3OT were nearly 450 C and 180.56 C, respectively.
This was similar to the reported melting point of 187 C and the glass
transition temperature of 100 C in a previous study [35]. Therefore, the
annealing temperature used in this study was less than 200 C. Fig. 7
shows the JSC and FF of the hybrid solar cell with POPT15 active layers
prepared at various annealing temperatures for 20 min under an AM1.5
illumination. Fig. 8 shows the efciency of the hybrid solar cell with
POPT15 active layers prepared at various annealing times for the xed
annealing temperature of 150 C under AM1.5 illumination. These results
show that the optimum annealing temperature and time were 150 C
and 20 min, respectively. This results indicate that optimum annealing
time can improve the nanoscale morphology and reordering of P3OT
molecular chains and thus increase the P3OT crystallinity, hole mobility,
and solar cell efciency [36,37]. Therefore, the best condition for fabricating P3HT: PCBM:TiO2 active layer for the device with the highest
efciency is 15 wt.% TiO2 content, 150 C annealing temperature, and
20 min annealing time. However, it is known that the P3HT-base solar
cells have a better efciency than those fabricated from P3OT [38,39].
It is because that the P3HT is the preferred donor material as it has
better hole mobility than P3OT (10 3 cm2 V1 s 1 for P3HT and
104 cm2 V1 s1 for P3OT) and also have lower band gap (1.9 eV)
enabling absorption in longer wavelength regime. The lower alkyl
chain length in P3HT compared to P3OT increases the electron density
and hence increases the electron donation possibility and favors the
1000
110 C
o
130 C
o
150 C
o
170 C
o
200 C
100
8000
10
-Z''/Ohm
10000
POPT0
POPT10
POPT15
POPT20
POPT25
0.1
0.01
1E-3
-2.0
6000
4000
2000
0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
Volatge (V)
Fig. 4. JV curves of Al/Ca/POPT/PEDOT:PSS/ITO hybrid solar cell obtained at (a) dark
and (b) AM1.5 illumination.
10000
20000
30000
Z'/Ohm
Fig. 5. AC impedance analysis of hybrid solar cell with POPT15 active layer obtained at
different annealing temperatures (110200 C) under AM1.5 illumination.
322
Y.-Y. Yu, C.-Y. Ciou / Thin Solid Films 544 (2013) 318323
(a)
2.5
100
2.0
90
Efficiency (%)
Weight (%)
80
70
60
50
1.5
1.0
0.5
40
30
0.0
20
0
0.2
30
40
50
60
0.0
20
Fig. 8. Efciency of hybrid solar cell with POPT15 active layer prepared at different
annealing times for xed annealing temperature 150 C under AM1.5 illumination.
(b) 0.4
-0.2
-0.4
-0.6
-0.8
-1.0
o
-1.2
Tm= 180.56 C
-1.4
0
50
100
150
200
250
300
350
400
Acknowledgment
Temperature (oC)
4. Conclusion
In conclusion, the addition of TiO2 NPs can enhance the efciency
of hybrid solar cells with P3OT:PCBM:TiO2 as an active layer by
50
6
45
5
4
40
35
FF (%)
Jsc (mA/cm2)
10
Temperature (oC)
2
30
1
25
0
0
50
100
150
200
250
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