Thin Solid Films 583 (2015) 8690

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Thin Solid Films

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

Efcient polymer:fullerene bulk heterojunction solar cells with n-type

doped titanium oxide as an electron transport layer
Youna Choi a, Geunjin Kim b, Heejoo Kim a,, Sun Hee Kim b, Kwanghee Lee a,b,
a
b

Heeger Center for Advanced Material & Research Institute of Solar and Sustainable Energies, Gwangju Institute of Science and Technology, Gwangju 500-712, Republic of Korea
School of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju 500-712, Republic of Korea

a r t i c l e

i n f o

Article history:
Received 4 November 2014
Received in revised form 3 March 2015
Accepted 25 March 2015
Available online 31 March 2015
Keywords:
Polymer solar cells
Electron transport layers
Titanium oxide
Solution process
Bulk heterojunction

a b s t r a c t
We have reported a highly n-type doped solution-processed titanium metal oxide (TiOx) for use as an efcient
electron-transport layer (ETL) in polymer:fullerene bulk heterojunction (BHJ) solar cells. When the metal ions
(Ti) in TiOx are partially substituted by niobium (Nb), the charge carrier density increased, by an order of
magnitude, because of the large electronegativity of Nb compared to that of Ti. Therefore, the work function
(WF) of Nb-doped metal oxide (Nb-TiOx) decreases from 4.75 eV (TiOx) to 4.66 eV (Nb-TiOx), leading to an
enhancement in the power conversion efciency (PCE) of BHJ solar cells with a Nb-TiOx ETL (from 7.99% to
8.40%).
2014 Elsevier B.V. All rights reserved.

1. Introduction
Bulk heterojunction (BHJ) solar cells composed of -conjugated
polymers (-CPs) and fullerenes have attracted considerable attention
as a promising energy source because of their low cost, solution processability, and large area obtained using roll-to-roll fabrication [1,2]. Over
the past decades, many efforts have been devoted to increasing the
power conversion efciency (PCE) of BHJ solar cells for commercial
applications [35]. Consequently, PCE of greater than 10% in BHJ solar
cells has recently been reported, indicating a promising outlook for
the commercialization of BHJ solar cells in the near future [4,5]. However, despite these impressive advancements, further improvement of the
PCE is still required. In general, PSCs use a structure of transparent
bottom electrode-BHJ layer-top cathode. Because of incompatibilities
at the interface of the active layer and electrodes, such as large contact
resistance and energy level mismatching between two layers, BHJ
solar cells frequently suffer an inefcient charge extraction from the
active layer to electrodes [6,7]. Therefore, one of the approaching ways
to improve the PCE of BHJ solar cells is to introduce an electron transport
layer (ETL) between the BHJ layer and the electrodes [8,9]. Interface
engineering by introducing the efcient ETL that can reduce charge
recombination at the interface and align the Fermi energy level between
the BHJ layer and the electrodes, plays a critical role in improving the
PCEs of BHJ solar cells.
Correspondence to: H. Kim, Tel.: +82 627153202; fax: +82 627153464.
Correspondence to: K. Lee, Tel.: +82 627152325; fax: +82 627153464.
E-mail addresses: heejook@gist.ac.kr (H. Kim), klee@gist.ac.kr (K. Lee).

http://dx.doi.org/10.1016/j.tsf.2015.03.061
0040-6090/ 2014 Elsevier B.V. All rights reserved.

During the past decades, numerous ETL materials based on transition metal oxides (TMOs) for efcient PSCs have been developed such
as titanium dioxides (TiO2), titanium sub-oxides (TiOx), and zinc oxide
(ZnO), and other transition metal oxide nanoparticles [9,10], because
of adjustable electronic structure of TMOs for aligning of the Fermi energy level between the BHJ layer and electrodes by developing doped
TMOs [11]. For example, by introducing dopant materials such as niobium (Nb) metal ions into TiO2, Ti metal ions can be substituted, altering
the electronic structure of TiO2. Thus, the doped TiO2 exhibits n-type
nature with increased charge carrier density and the reduced work
function (WF) values [11]. Furthermore, because Nb, which is a groupV dopant for TiO2, has a higher number of valence electrons and similar
ionic sizes compared to Ti [12,13], the original crystalline structure of
TiO2 can be preserved and similar optical properties were observed in
Nb-doped TiO2 [14,15]. However, crystalline TiO2 layers should be prepared at high temperature above 450 C or by complex synthetic steps
[12,16]. Furthermore, to synthesize the doped TiO2 system, it is also
required the harsh process such as sintering process [1619], complex
purications, and long reaction time for 20 h [19]. Because such difculties in the utilizing TiO2 are incompatible with PSCs, which are fabricated by solution process with low-temperature, it is required to develop a
low-temperature and solution-processable titanium oxide.
Solgel processed amorphous TiOx is one of the promising ETLs for
PSCs because of its excellent air-stability, charge transport, charge
selectivity, and good wettability on organic layers [9,20]. In addition,
solgel processed TiOx can be synthesized using a simple synthetic
method under low-temperature processing in a short reaction time.
However, since the oxygen deciency related doping of TiOx is

Y. Choi et al. / Thin Solid Films 583 (2015) 8690

uncontrollable under the ambient air, other reliable doping process of

the TiOx should be required for efcient ETL. Therefore, in this work,
we developed hetero metal atom doped metal titanium oxide, Nbdoped TiOx, by introducing Nb ion as dopant in solgel synthesis of
TiOx with easy and low-temperature process. The resulting Nb-doped
TiOx showed the improved n-type characters compared with TiOx: the
reduced WF value and the increased charge carrier density. The NbTiOx ETL improves the electrical contact between BHJ layer and metal
cathode by reducing the charge recombination in the BHJ layer and
facilitating charge extraction from BHJ layer to the metal cathode.
Therefore, PSC with Nb-TiOx ETL exhibited better device performance
than device with pristine TiOx ETL.

2. Experimental details
2.1. Materials
TiO x was synthesized using a solgel procedure with titanium
(IV) isopropoxide (Ti[OCH(CH3 )2 ] 4 , Aldrich, 99.999%, 2 mL), 2methoxyethanol (CH3OCH2CH2OH, Aldrich, 99.9 + %, 10 mL) and
ethanolamine (H2NCH2CH2OH, Aldrich, 99 + %, 1 mL). All materials
were mixed for 5 min at RT. After this step, the precursor was reuxed
for 1 h at 120 C to remove the solvent. All procedures were performed
under a N2 atmosphere.
Nb-doped TiOx was synthesized using a solgel procedure with
titanium (IV) isopropoxide (Ti[OCH(CH3)2]4, Aldrich, 99.999%, 2 mL),
niobium ethoxide (Nb[OCH2CH3]5, Alfa Aesar, 99.999%, 22 mg), 2methoxyethanol (CH3OCH2CH2OH, Aldrich, 99.9 + %, 10 mL) and
ethanolamine (H2NCH2CH2OH, Aldrich, 99 + %, 1 mL). To synthesize
Nb-TiOx, niobium ethoxide was mixed with titanium (IV) isopropoxide
with a 1 mol.% ratio of Nb to Ti. All materials were mixed for 5 min at RT.
After this step, the precursor was reuxed for 1 h at 120 C to remove
the solvent. All procedures were performed under a N2 atmosphere.
The synthesized TiOx and Nb-TiOx precursor solutions were diluted
with methanol (1:200 by weight). The chemical structures of TiOx and
Nb-TiOx are presented in Fig. 1a.

87

2.2. Device fabrication

BHJ solar cells were fabricated on a pre-cleaned indium tin
oxide (ITO)/glass substrate. An aqueous solution of poly(3,4ethylenedioxythiophene):poly(styrene sulfonate), PEDOT:PSS(VPAI
4083, H. C. Stark), was spin coated as a hole-transport layer (HTL).
The ITO/PEDOT:PSS substrates were dried for 10 min at 150 C in air
and then transferred into a glove-box to spin-cast the active layer. A
mixture of poly(thieno[3,4-b]thiophene-alt-benzodithiophene) derivative (PTB7-Th) and a fullerene derivative, [6,6]-phenyl-C71-butyric acid
methyl ester (PC70BM) as an acceptor (1:1.5 by weight) in chlorobenzene solvent with diiodooctane (DIO) additive (3 vol.%) was spin-cast
on top of the PEDOT layer. PTB7-Th and PC70BM were purchased from
1-Materials, Inc. and Nano-C, Inc., respectively. Then, a diluted precursor solution of TiOx or Nb-TiOx was spin-cast in air on top of the active
layer. Next, the device was pumped down to vacuum (107 Torr), and
a ~ 100 nm thick Al electrode was deposited. The device structure and
the chemical structures of PTB7-Th and PC70BM are illustrated in Fig. 1b.
2.3. Measurements
Current densityvoltage (JV) curves were measured using a
Keithley 237 source meter under Air Mass 1.5 Global (AM 1.5 G) irradiation from a calibrated solar simulator with an irradiation intensity of
100 mW/cm2. The capacitancevoltage (CV) measurement was
performed using a semiconductor parameter analyzer (HP4284A) and
LCR meter. The WF values of TiOx and Nb-TiOx lms were measured
using a Kelvin probe (KP 6500 Digital Kelvin probe, McAllister Technical
Services. Co. Ltd) under atmospheric conditions.
3. Results and discussion
3.1. Properties of Nb-doped TiOx lms
Fig. 2a presents the UVVis absorption spectra of the TiOx and Nbdoped TiOx lms. Because we added 1 mol.% Nb to TiOx, the absorption

Fig. 1. (a) The chemical structures of TiOx and Nb-TiOx. (b) The device structure of PTB7-Th:PC70BM BHJ solar cells and the chemical structures of PTB7-Th and PC70BM.

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Y. Choi et al. / Thin Solid Films 583 (2015) 8690

Fig. 2. (a) UVVis absorption spectra of TiOx and Nb-TiOx lms. (b) XPS spectra of TiOx and Nb-TiOx lms. Inset is the high-resolution XPS spectrum for Nb3d on the Nb-TiOx lm.

spectra of TiOx and Nb-TiOx were almost identical with a well-dened

absorption edge at approximately 335 nm (~ 3.7 eV). Fig. 2b presents
the X-ray photoelectron spectra (XPS) of the TiOx and Nb-doped TiOx
lms. Note that the XPS survey scans were almost identical for each
lm. The XPS peaks located at 284 eV, 458 eV and 530 eV can be
attributed to C1s, Ti 2p, and O1s binding energies, respectively [21].
However, in the high-resolution XPS spectra (inset of Fig. 2b), we
could identify two distinct peaks in the Nb-TiOx lm. These two
peaks correspond to the presence of the Nb5 + oxidation state with a
Nb 3d5/2 binding energy of 205.0 eV and to the Nb3 + oxidation state
with a Nb 3d3/2 binding energy of 209.4 eV [22,23]. Therefore, the
results from the XPS spectra indicate that Nb ions were incorporated
in TiOx without any additional treatments such as a high temperature
(N450 C) or difcult synthetic process as reported previously [1619].

3.2. Electrical properties

To clarify the improved n-type nature of Nb-TiOx, Kelvin probe
(KP) measurements were performed on two lms. The results were
compared with the WF values of the n-doped systems (TiOx and NbTiOx). The samples were prepared on an ITO substrate for the KP
measurements. Fig. 3a presents the measured WF values and statistical
distributions for TiOx, and Nb-TiOx, respectively. The average WF values
are summarized in Table 1. It is clearly observed that the Nb-TiOx
exhibited reduced WF value (4.66 eV) in comparison with that of TiOx
(4.75 eV), which is typical character of enhanced n-type doped
semiconductors [24].

The carrier density of Nb-TiO x was measured by CV measurements on the ETLs, with the structure of ITO/metal oxide (TiOx, and
Nb-TiOx)/Al, at room temperature in air under dark condition [25].
ITO was used as a bias electrode. Fig. 3b presents the 1 / C2 V
characteristic curves for the TiO x and Nb-TiOx lms. The relation
between the charge carrier density and 1 / C2 is given by the following
equation, as obtained from Schottky junction theory [25,26]:
2

1=C 2Vbi V=qr 0 Nd

where Vbi is the built-in potential, V is the applied voltage, q is the

elementary charge, 0 is the vacuum permittivity, r is the relative
permittivity of the sample, and Nd is the ionized donor concentration
in the depletion layer. The r value for each lm was derived using the
equation for a parallel plate capacitor [24]. Through linear tting with
1 / C2 as function of 2(Vbi V) / qr0Nd, the Nd values for each lm
were obtained (Table 1). Note that the insertion of Nb into TiOx
increases the Nd value from 5.6 1017 cm 3 to 1.2 1018 cm 3.
Because the Nd value is consistent with the electron concentration in
the depletion layer, the increased Nd value of Nb-TiOx (~ 1018 cm3)
compared to that of TiOx (~ 1017 cm3) indicates the development of
n-type character in Nb-TiOx. This variation trend of the Nd values is in
good agreement with that of the WF values for TiOx and Nb-TiOx, as
presented in Fig. 3a. Therefore, these results demonstrate that Nb-TiOx
is a highly n-type doped system that can be applied as an efcient ETL
for BHJ solar cells. It is noticeable that this hetero metal atom doping
was achieved in the amorphous system, which is utilized a solgel
process with easy and low-temperature process compared to those of

Fig. 3. (a) The measured WF values of TiOx, and Nb-TiOx lms. (b) 1 / C2 V characteristic curves for TiOx, and Nb-TiOx lms. (c) Energy level diagrams of PTB7-Th:PC70BM BHJ solar cells
with various ETL materials.

Y. Choi et al. / Thin Solid Films 583 (2015) 8690

Table 1
The relative permittivities (r), charge carrier densities (Nd), and work function values of
TiOx and Nb-TiOx lms.

TiOx
Nb-TiOx

Nd (cm3)

WF (eV)

9.04
15.3

5.6 1017
1.2 1018

4.75
4.66

89

Table 2
Performance of BHJ solar cells without TiOx and with TiOx and Nb-TiOx layer.
ETL

Voc (V)

Jsc (mA cm1)

FF

PCE (%)a

No
TiOx
Nb-TiOx

0.65 (0.65)
0.77 (0.74)
0.77 (0.76)

14.52 (14.27)
15.27 (14.99)
16.05 (15.76)

0.57 (0.57)
0.68 (0.66)
0.68 (0.68)

5.38 (5.28)
7.99 (7.40)
8.40 (8.16)

a
The device parameters show the best values of each type. The values in parentheses
are average values from 20 devices of each type.

the crystalline systems [16,19]. Based on the KP and CV measurements, we summarized the schematic energy level diagram for PTB7Th:PC70BM BHJ solar cells with various ETLs (TiOx, and Nb-TiOx), as
shown in Fig. 3c.
3.3. Performance of polymer solar cells
To conrm that Nb-TiOx functions as an ETL, we compared the JV
characteristics of PTB7-Th:PC70BM BHJ solar cells without and with
TiOx and Nb-TiOx (see Fig. 4a and Table 2). In contrast with the previous
reports [16,19], additional process such as high annealing temperature
has not been applied on the device with ETL (see the experimental
details) because ETL has excellent n-type doped characters even at
low temperature process as described previously. The device without
ETL exhibited a PCE of 5.38% with a short circuit current (Jsc) of
14.52 mA/cm2, a Voc of 0.65 V, and a ll factor (FF) of 0.57. However,
the introduction of the ETL into the BHJ solar cells resulted in a signicant improvement. The device with TiOx exhibited a PCE of 7.99% with
an increased Jsc value of 15.27 mA/cm2 (FF = 0.68). Furthermore,
when the Nb-TiOx layer was used as the ETL, the device exhibited the
highest PCE of 8.40% with a Jsc = 16.05 mA/cm2 and a FF = 0.68.
Because the Voc and FF of all of the devices were almost identical, it
can be concluded that the Jsc is the main factor for enhancing the PCE
in BHJ solar cells that incorporate Nb-TiOx.
To understand the high Jsc value of BHJ solar cells with Nb-TiOx, we
studied the recombination kinetics in the BHJ solar cells using the
light intensity dependent JV characteristics, which can prove the
recombination kinetics in the BHJ solar cells [2729]. Fig. 5a presents a
semi-logarithmic plot of Voc as a function of incident light intensity for
BHJ solar cells without and with ETLs (TiOx, Nb-TiOx). The slope of the
Voc versus the light intensity can be derived from the following equation [27,28]:
V oc kB T=e ln I const:

where I is the incident light intensity, kB is the Boltzmann constant,

T is the temperature in Kelvin, and e is the elementary charge. When
bimolecular recombination, which is the recombination of mobile

electrons and holes at the interface of the donor/acceptor heterojunction,

is dominant, the slope of the Voc versus the logarithm of the light
intensity gives kBT/e. On the other hand, the slope of monomolecular
recombination such as ShockleyReadHall (SRH) recombination,
which is a trap-assisted recombination for an electron and a hole in
the materials, shows a strong Voc dependence [27]. As in Fig. 5a, the
BHJ solar cell without ETL yields 1.45 kBT/e, implying that, at open
circuit, the monomolecular recombination is dominant. However, the
slopes for the device with TiOx are 1.26 kBT/e, indicating the signicant
reduction of interfacial traps at the interface between the active layer
and Al cathode by introducing TiOx despite its deeper WF value of
TiOx than that of Al electrode. In the device with Nb-TiOx, more reduction of the trap assisted recombination was observed with a closer
value to kBT/e (1.22 kBT/e). Because the WF of Nb-TiOx was reduced,
this decrease in the slope can be attributed to the reduced WF value
of Nb-TiOx compared to that of TiOx.
The charge recombination mechanism of the BHJ solar cells at
the short circuit is also investigated by utilizing the variation of Jsc as a
function of incident light intensity. The Jsc is correlated to the following
equation [29]:

Jsc I 1

The exponential factor = 1 indicates bimolecular recombination

[30]. Fig. 5b shows the loglog plot of Jsc versus I. For the device without
ETL, the tting of data yields = 0.960. However, the use of TiOx and
Nb-TiOx leads to the increased in the device (0.964 for TiOx, 0.970
for Nb-TiOx). In particular, a closer value to unity in the device with
Nb-TiOx is indicative that bimolecular recombination is minimized
and the sweep-out is the most efcient in the device. Therefore, the
highest Jsc value in the BHJ solar cell with Nb-TiOx is likely responsible
for the signicant reduction of the interfacial traps assisted recombination with efcient sweep-out in the device by introducing the highly
n-doped ETL. Therefore, it can be concluded that the reduced WF value
and the increased charge carrier density in the Nb-TiOx improve the
PCE of BHJ solar cells by facilitating charge extraction and reducing

Fig. 4. (a) The JV characteristics of the PTB7-Th:PC70BM BHJ solar cells without TiOx, with TiOx and with Nb-TiOx layers under AM 1.5 G irradiation. (b) External quantum efciency (EQE)
spectra of the PTB7-Th:PC70BM BHJ solar cells without TiOx, with TiOx and with Nb-TiOx layers.

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Y. Choi et al. / Thin Solid Films 583 (2015) 8690

Fig. 5. (a) Open-circuit voltage as a function of light intensity; PTB7-Th:PC70BM BHJ solar cells without TiOx, with TiOx and with Nb-TiOx layers. (b) Short-circuit current density as a
function of light intensity; PTB7-Th:PC70BM BHJ solar cells without TiOx, with TiOx and with Nb-TiOx layers.

recombination at the interface, as observed in the JV characteristics of

BHJ solar cell with Nb-TiOx.
4. Conclusion
We developed a highly n-type doped, low-temperature solution
processable Nb-TiOx as an efcient ETL material for BHJ solar cells. By
introducing Nb ions to partially substitute for Ti ions in TiOx, highly ntype doped Nb-TiOx was easily synthesized without any post treatment
of metal oxide, which processed a 2-fold improved charge carrier
density and a reduced WF value. Therefore, the use of Nb-TiOx as an
ETL signicantly reduces the charge recombination at the interface
between the metal electrode and the active layer in the BHJ solar cell
structure, leading to an enhancement in PCE compared to that of the
device with TiOx. Therefore, our results provide a route to tailor the
electronic properties of transition metal oxides that can improve the
PCEs of BHJ solar cells as ETLs.
Acknowledgments
This project was supported by the Core Technology Development
Program for Next-Generation Solar Cells of the Research Institute for
Solar and Sustainable Energies (RISE) at GIST and the National Research
Foundation of Korea (NRF) grant funded by the Korea government
(MSIP) (NRF-2014R1A2A1A09006137). The authors also acknowledge
the support provided by the National Research Foundation of Korea
(NRF) grant funded by the Korea government (MSIP) (No. 20080062606, CELA-NCRC).
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