Photocurrent response wavelength up to 1.

1μm from photovoltaic cells

based on narrow-band-gap conjugated polymer and fullerene derivative
Yangjun Xia, Li Wang, Xianyu Deng, Dongyun Li, Xuhui Zhu et al.

Citation: Appl. Phys. Lett. 89, 081106 (2006); doi: 10.1063/1.2338017

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 APPLIED PHYSICS LETTERS 89, 081106 共2006兲

Photocurrent response wavelength up to 1.1 ␮m from photovoltaic

cells based on narrow-band-gap conjugated polymer
and fullerene derivative
Yangjun Xia, Li Wang, Xianyu Deng, Dongyun Li, Xuhui Zhu, and Yong Caoa兲
Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology,
Guangzhou 510640, People’s Republic of China and Key Laboratory of Special Functional Materials, South
China University of Technology, Guangzhou 510640, People’s Republic of China
共Received 1 May 2006; accepted 17 July 2006; published online 22 August 2006兲
An extremely narrow-band-gap conjugated polymer poly共5,7-bis共4-decanyl-2-thienyl兲thieno关3,4-
b兴diathiazole-thiophene-2,5兲 共PDDTT兲 共Eg ⬇ 1.01 eV兲 was synthesized by Stille coupling reaction,
which absorbs the light from 330– 1220 nm in solid thin film and shows good solution
processibility. The polymeric photovoltaic cells based on PDDTT/关6,6兴-phenyl-C61-butyric acid
methyl ester blend show the short circuit density of 0.83 mA/ cm2, open current voltage of 0.35 V,
and photocurrent spectra response from 330 to 1100 nm under AM 1.5 simulator
共100 mW/ cm2兲. © 2006 American Institute of Physics. 关DOI: 10.1063/1.2338017兴

Since the discovery of the ultrafast photoinduced charge photocurrent response wavelength exceeding over 1000 nm
transfer between conjugated polymer and fullerene,1 poly- were not reported by now.
meric photovoltaic devices have attracted much attention for In this letter, we reported photovoltaic cells that used a
the potential application for large-area, flexible, and low-cost narrow-band-gap conjugated polymer 共poly关5,7-bis共4-
solar cells.2–5 Many approaches have been employed to decanyl-2-thienyl兲thieno关3,4-b兴diathiazole-thiophene-2,5兴
achieve higher power conversion efficiency in plastic solar 共PDDTT兲 共Eg = 1.01 eV兲 as electron donor material and
cells. Although bulk heterojunction devices with interpen- PCBM as electron acceptor material. The PPVCs based on
etrating networks of a conjugated polymer as electron donor the PDDTT/PCBM blend show a short circuit density 共Jsc兲 of
and a fullerene derivative, 关6,6兴-phenyl-C61-butyric acid me- 0.83 mA/ cm2, an open current voltage 共Voc兲 of 0.35 V, a fill
thyl ester 共PCBM兲 as electron acceptor have achieved power factor 共FF兲 of 38.6% under AM 1.5 simulator
conversion efficiency up to 4%–5%,6,7 the general 共100 mW/ cm2兲, and photocurrent response wavelengths up
conjugated polymers used in photovoltaic solar cells that ab- to 1100 nm from photovoltaic solar cells based on the
sorb light range from 300 to 650 nm,8 are mismatched with PDDTT/PCBM blend.
the solar terrestrial radiation 共300– 1500 nm, with maximal PDDTT was synthesized from 5,7-bis共5-bromo-
flux at 690 nm兲.9 The narrow-band-gap conjugated polymers 4-decanyl-2-thienyl兲thieno关3,4-b兴diathiazole and 2,5-
with high absorption coefficient and broad absorption bis共tri-n-butyltin兲thiophene by palladium-catalyzed
spectra are promising for the development of high Stille coupling reaction. 5,7-bis共5-bromo-4-decanyl-
performance photovoltaic solar cells due to the improved 2-thienyl兲thieno关3,4-b兴diathiazole were synthesized from
harvest of the solar emission.8 Recently, Brabec et al.5 5,7-bis共4-decanyl-2-thienyl兲thieno关3,4-b兴diathiazole 共Ref.
13兲 by brominating with N-bromosuccinimide.14 2,5-bis共tri-
reported a narrow-band-gap alternating copolymer poly
n-butyltin兲thiophene were synthesized by the procedure re-
共Ndodecyl-2,5-bis共2-thienyl兲pyrrole-共2,1,3-benzothiadiazole兲
ported in Ref. 15. PCBM was synthesized by the procedure
共PTPTB兲 derived from N-dodecyl-2,5-bis共2-thienyl兲pyrrole
of in Ref. 16. The PDDTT and monomers were characterized
and 2⬘ , 1⬘ , 3⬘-benzothiadiazole which has a band gap of
by 1H NMR spectra 共Bruker DRX 300 spectrometer operat-
around 1.77 eV.9 The photovoltaic device based on the blend
ing at 300 MHz兲 and Elemental analyses 共performed on a
of PTPTB and PCBM showed a photocurrent spectral re- vario EL Elemental Analysis Instrument, Elementar Co.兲.
sponse with light wavelength up to 750 nm, current density The number molecule weight of PDDTT is about
of 3.1 mA/ cm2, and power conversion efficiency of 1%. We 6800 g / mol 共measured on a Waters GPC 2410 in tetrahydro-
reported photovoltaic cells based on narrow band gap furan 共THF兲 via a calibration curve of polystyrene stan-
fluorene-based conjugated copolymer and PCBM blend dards兲. The absorption spectra of PDDTT in THF solution
which showed moderate performance with photocurrent re- and in solid thin film were measured on a Perkin-Elmer
sponse up to 780 nm.10 Zhang et al.11 reported polymeric Lambda-9 spectrophotometer. Cyclic voltammetry was mea-
photovoltaic cells 共PPVCs兲 based on alternating polyfluorene sured on a potentiostat/galvanostat model 283 electrochemi-
共APFO兲-Green2/PCBM blend with photocurrent response cal workstation 共Princeton Applied Research兲 at a scan rate
wavelength up to 850 nm. Lately, a photovoltaic device of 50 mV/ s with a nitrogen-saturated solution of 0.1M tet-
based on the blend of PCBM and narrow-band-gap conju- rabutylammonium hexafluorophosphate 共Bu4NPF6兲 in aceto-
gated polymer 共APFO-Green1兲 reported by Wang et al.12 has nitrile 共CH3CN兲, with platinum and saturated calomel elec-
extended the light response to 1000 nm. But the PPVCs with trodes as the working and reference electrodes.
Photovoltaic solar cells were fabricated using a sand-
a兲
Author to whom correspondence should be addressed; electronic mail: wich structure of indium tin oxide 共ITO兲/
[email protected] polyethylenedioxythiophene polystyrene sulfonic acid

0003-6951/2006/89共8兲/081106/3/$23.00 89, 081106-1 © 2006 American Institute of Physics

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081106-2 Xia et al. Appl. Phys. Lett. 89, 081106 共2006兲

FIG. 2. Electrochemical characteristic of PDDTT.

Jm ⫻ Vm
FF = , 共2兲
Jsc ⫻ Voc
where Pin is the incident radiation flux, Jsc and Voc are the
short circuit current density and open circuit voltage, respec-
FIG. 1. 共a兲 Chemical structures of PDDTT and PCBM; 共b兲 normalized tively and Jm and Vm are the current density and voltage at
absorption spectra of PDDTT in solid thin film and in the THF solution the maximum power output, respectively.
共5 ⫻ 10−5兲.
Figure 1 shows the normalized UV-vis absorption of the
polymers in the solution of THF 共5 ⫻ 10−5 mol/ L兲 and solid
共PEDOT:PSS兲/PDDTT:PCBM blend/Ba/ Al on prepatterned thin film. There are two absorption peaks at around 401 and
ITO with a sheet resistance of 10– 20 ⍀ / 䊐. The substrate 714 nm in the solution of THF. There are two absorption
was ultrasonically cleaned with acetone, detergent, de- peaks at around 479 and 865 nm in solid thin film. The large
ionized water, and 2-propanol subsequently. Oxygen plasma redshift observed when going from a solution to a solid thin
treatment was made for 10 min as the final step of substrate film are similar to that observed for poly共3-alkylthiophenes兲
cleaning to improve the contact angle just before film coat- and interchain interactions in the solid state, possibly assisted
ing. Onto the ITO glass, a layer of PEDOT:PSS film with a by planarization and an increase of conjugation length.17 The
thickness of 50 nm was spin coated from its aqueous disper- onset wavelength of PDDTT in solid thin film is about
1220 nm and the optical band gap of PDDTT is about
sion 共Baytron P4083, Bayer AG兲, aiming at improving the
1.01 eV.
hole injection and avoiding the possibility of leakage.
The onset of oxidation potential of the PDDTT is about
PEDOT:PSS film was dried at 80 ° C for 2 h in the vacuum
0.31 V and the onset of reduction potential is about −0.81 V
oven. The solution of the PDDTT and PCBM with different
共Fig. 2兲. The highest occupied molecular orbital 共HOMO兲
weight ratios in toluene was prepared in a nitrogen-filled dry
and lowest unoccupied molecular orbital 共LUMO兲 levels of
box and spin coated on the top of the ITO/PEDOT:PSS sur- the PDDTT, calculated by empirical formulas EHOMO
face. The typical thicknesses of the PDDTT/PCBM blend = −e共Eox + 4.4兲 共eV兲 and ELUMO = −e共Ered + 4.4兲 共eV兲,18 were
layer were 70– 80 nm. Then a thin layer of barium and the about −4.71 and −3.59 eV, respectively. The electrochemical
subsequent 200 nm thick aluminum capping layers were band gap of PDDTT is about 1.12 eV is slightly higher than
thermally deposited by vacuum evaporation through a mask the optical band gap of PDDTT 关1.01 eV, Fig 1共b兲兴.
at a base pressure below 2 ⫻ 10−4 Pa. The deposition speed The device characteristics of PDDTT- and PDDTT/
and thickness of the barium and aluminum layers were moni- PCBM-based photovoltaic cells are presented in Table I. As
tored by a thickness/rate meter 共model STM-100, Sycon兲. shown in Table I, the short current 共Jsc兲 of the PPVCs based
The cathode area defines the active area of the device. The on the PDDTT/PCBM blend are increased about 200 times
typical active area of the devices in this study is 0.15 cm2. that of the PPVCs based on pristine polymer, while Voc drops
The spectral response was measured with a commercial pho- after the addition of more than 50% PCBM 共Table I兲. van
tomodulation spectroscopic setup 共Oriel兲. A calibrated Si Duren et al.19 have shown that saturating the active layer
photodiode was used to determine the photosensitivity. En- with PCBM leads to a decrease in the Jsc due to phase sepa-
ergy conversion efficiencies were measured under an AM 1.5 ration. The bulk heterojunction photovoltaic device based on
solar simulator 共100 mW/ cm2兲. The current-voltage 共I-V兲
characteristics of PVCs were measured with a Keithley 236 TABLE I. Device characteristics of PDDTT and PDDTT/PCBM-based pho-
source-measure unit. The power conversion efficiency 共␩e兲 tovoltaic cells.
and fill factor 共FF兲 were calculated by the following equa-
tions: Voc Isc FF ␩e
Device 共V兲 共mA/ cm2兲 共%兲 共%兲

Pure PDDTT 0.5 0.004 15.5 3.1⫻ 10−4

PDDTT:PCBM 共1:1兲 0.35 0.83 38.6 0.11
FF ⫻ Jsc ⫻ Voc
␩e = , 共1兲 PDDTT:PCBM 共1:3兲 0.30 0.68 33.2 0.07
Pin
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081106-3 Xia et al. Appl. Phys. Lett. 89, 081106 共2006兲

DTT was soluble in common organic solvent, and shows

wide light absorption ranges of 330–1000 and 330– 1220 nm
in THF solution and solid thin film, respectively. The elec-
trochemical band gap was determined at about 1.12 eV. The
PPVCs based on the PDDTT/PCBM 共1:1兲 blend show a
short circuit density of 共Jsc兲 0.83 mA/ cm2, an open current
voltage 共Voc兲 of 0.35 V, and a fill factor 共FF兲 of 38.6% under
A.M 1.5 simulator 共100 mW/ cm2兲. The photocurrent re-
sponse wavelengths of the PPVCs based on PDDTT/PCBM
blends extend to about 1100 nm.
The authors are deeply grateful to the National Natural
Science Foundation of China 共Project No. 50433030兲 and the
MOST National Research Project 共No. 2002CB613405兲 for
financial support.
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