Published: November 08, 2011
pubs.acs.org/Macromolecules
Crystalline Low-Band Gap Polymers Comprising Thiophene and
2,1,3-Benzooxadiazole Units for Bulk Heterojunction Solar Cells
Jian-Ming Jiang, Po-An Yang, Tsung-Hsuan Hsieh, and Kung-Hwa Wei*
Department of Materials Science and Engineering, National Chiao Tung University, 300 Hsinchu, Taiwan
’ INTRODUCTION
Thin-film polymer solar cells (PSCs) based on bulk hetero-junction (BHJ) structures incorporating (i) conjugated polymers possessing delocalizedπ electrons and (ii) fullerenes are being studied extensively because they allow the fabrication of light-weight, large-area,flexible devices using low-cost solution processing methods.14 Regioregular polythiophene derivatives have been widely investigated for BHJ devices because of their high crystal-linity, good light harvesting in the visible spectrum, and excellent carrier mobility.58Nevertheless, the power conversion efficiencies (PCEs) of such systems are difficult to improve upon because of the limited absorption at wavelengths of less than 650 nm9 and because the open-circuit voltage (Voc) is limited at
approx-imately 0.6 V.
In attempts to harvest more photons and to tune the energy levels, several conjugated polymers have been developed featur-ing electron donor/acceptor (D/A) units in the main chain conjugated configurations1016and side chainattached
archi-tectures.1720Recently, some new lowband gap polymers have exhibited PCEs of up to 7%.2125To obtain high-performance photovoltaic polymer materials, it will be necessary to synthesize conjugated polymers with several ideal properties: low band gaps to broaden the absorption range; crystalline characteristics to ensure good charge mobility; low highest occupied molecular orbital (HOMO) energy levels to enhance the values of Voc; and
suitable lowest unoccupied molecular orbital (LUMO) energy levels for efficient electron transfer to the fullerene moieties.
Strong electron-withdrawing units are necessary when choos-ing an acceptor unit to lower the LUMO energy level of a D/A polymer. With a proper selection of the acceptor, however, both
the HOMO and LUMO energy level of the synthesized polymer can be decreased. Benzothiadiazole (BT) is one of the stronger electron-withdrawing moieties used widely in PSCs exhibit-ing PCEs of up to 56%,26
due to a combination of its electron accepting properties and its ability to adopt a quinoid structure, resulting in lowband gap, coplanar polymers. Replacing the sulfur atom with an oxygen atom forms benzooxadiazole (BO), which can decrease both the HOMO and LUMO energy levels;27 this molecular structure not only can result in air-stable poly-mers but also produce high open-circuit potentials when blended with fullerenes.28Some polymers based on BO units, however, provide low PCEs—presumably the result of their relatively low molecular weights and low solubility,27,29while other polymers incorporating BO units had decent molecular weight and exhibited good device PCE using additives.30 To solve this problem, we designed a soluble acceptor31 by introducing two octyloxy chains on the BO ring.
In this study, we selected several thiophene-based building blocks so that our D/A polymers would feature not only strong and broad absorption (i.e., good harvesting of sunlight) but also suitable molecular energy levels to ensure good charge separation and transportation as well as high open-circuit voltages. Further-more, we expected the development of new D/A polymers exhibiting crystalline characteristics to lead to significantly enhanced charge mobilities in the active layers of the devices. Several p-type conjugated polymers containing the symmetrical
Received: August 12, 2011 Revised: October 18, 2011 ABSTRACT:We have used Stille coupling polymerization to
synthesize a series of new crystalline lowband gap conjugated polymers—PTHBO, PBTTBO, and PTTTBO—constituting mainly electron-rich thiophene (TH), 2,20-bithiophene (BT), and thieno[3,2-b]thiophene (TT) units in conjugation with electron-deficient 2,1,3-benzooxadiazole (BO) moieties. All of these polymers exhibited (i) sufficient energy offsets with respect to those of fullerenes to allow efficient charge transfer and (ii) low-lying highest occupied molecular orbital (HOMO,5.47 eV). These polymers exhibited excellent thermal stability, high crystal-linity, and broad spectral absorptions. As a result, bulk hetero-junction photovoltaic devices derived from these polymers and
fullerenes provided open-circuit voltages (Voc) as high as 1.02 V. In particular, the photovoltaic device comprising the PTTTBO/
PC61BM (1:1) blend system and 1,8-diiodooctane (DIO, 0.5 vol %) as an additive exhibited excellent performance, under AM 1.5 G
irradiation (100 mW cm2), with a value of Vocof 0.85 V, a short-circuit current density (Jsc) of 11.6 mA cm2, afill factor (FF) of
thiophene, bi(alkyl)thiophene3234 and 3,6-dialkylthieno[3,2-b]thiophene35 exhibit crystalline characteristics and high hole mobilities when used in organicfield effect transistors. Consider-ing not only electronic energy levels but also hole mobilities, we prepared a series of new D/A polymers—PTHBO, PBTTBO, and PTTTBO—wherein electron-withdrawing BO units were conjugated with the symmetrical electron-donating units to provide crystalline characteristics and a low-lying HOMO energy levels. Because of these desirable features, we expected PTHBO, PBTTBO, and PTTTBO to exhibit good hole mobilities and high values of Vocwhen used in photovoltaic applications.
’ EXPERIMENTAL SECTION
Materials and Synthesis. 2,5-Bis(trimethylstannyl)thiophene (M3),36(4,40-dioctyl-2,20-bithiophene-5,50-diyl)bis(trimethylstannane) (M4),32and (3,6-dioctylthieno[3,2-b]thiophene-2,5-diyl)bis(trimethy-lstannane) (M5)13 were prepared according to reported procedures. [6,6]-Phenyl-C61-butyric acid methyl ester (PC61BM) was purchased
from Nano-C. All other reagents were used as received without further purification, unless stated otherwise.
1,2-Bis(octyloxy)benzene(1). A mixture of catechol (10 g, 0.091 mol), 1-bromooctane (40 g, 36 mL, 0.21 mol), and K2CO3(38 g, 0.27
mol) in dry DMF (50 mL) was stirred at 100°C under a N2atmosphere
for 40 h. After cooling to room temperature, water (300 mL) was added; the organic layer was separated and the aqueous layer extracted with CH2Cl2. The combined organic phases were dried (MgSO4) and
concentrated under reduced pressure. The crude product was purified through column chromatography (SiO2, hexane) to provide a colorless
oil (27 g, 90%).1H NMR (300 MHz, CDCl3):δ 6.89 (s, 2H), 3.99 (t, J =
6.9 Hz, 4H), 1.841.77 (m, 4H), 1.491.29 (m, 20H), 0.90 (t, J = 6.7 Hz, 6H).13C NMR (75 MHz, CDCl3):δ 149.1, 120.9, 114.0, 69.2, 31.8,
29.4, 29.3, 29.2, 26.0, 22.6, 14.0.
1,2-Dinitro-4,5-bis(octyloxy)benzene(2). A 65% HNO3(20 mL)
sample was added dropwise to a two-neck round-bottom flask contain-ing 1,2-bis(octyloxy)benzene (10 g, 30 mmol), CH2Cl2(140 mL), and
AcOH (140 mL), cooled at 10°C . The reaction mixture was warmed to room temperature and stirred for 1 h. The mixture was then cooled to 10°C and 100% HNO3(50 mL) was added dropwise. The mixture was
warmed to room temperature and stirred for 40 h before being poured into icewater. The CH2Cl2layer was separated and the aqueous phase
extracted with CH2Cl2. The organic phases were combined, washed
sequentially with water, sat. NaHCO3(aq), and brine, and then dried
(MgSO4). Concentration under vacuum gave a crude product that
was recrystallized from EtOH. Yield: 12 g (95%).1H NMR (300 MHz, CDCl3):δ 7.29 (s, 2H), 4.09 (t, J = 6.6 Hz, 4H), 1.911.81 (m, 4H),
1.491.28 (m, 20H), 0.89 (t, J = 6.9 Hz, 6H).13
C NMR (75 MHz, CDCl3): δ 151.7, 136.4, 107.8, 74.7, 31.7, 30.1, 29.4, 29.2, 25.7,
22.6, 14.1.
5,6-Bis(octyloxy)benzo[ c][1,2,5]oxadiazole (3). A mixture of 1,2-dinitro-4,5-bis(octyloxy)benzene (2, 848 mg, 2.00 mmol), NaN3(650 mg,
10.0 mmol), and n-Bu4NBr (130 mg, 0.400 mmol) was heated under
reflux in toluene (10 mL) for 12 h. At this point, the starting material had been consumed (TLC); PPh3(630 mg, 2.40 mmol) was added and the
mixture heated under reflux for an additional 24 h. The reaction mixture was cooled to room temperature and filtered through a short silica plug; the plug was rinsed with CH2Cl2. Evaporation of the solvents from the
combined organic phases, under reduced pressure, afforded a crude solid that was recrystallized (EtOH) to yield an off-white solid (683 mg, 63%).
1 H NMR (300 MHz, CDCl3):δ 6.79 (s, 2H), 4.05 (t, J = 6 Hz, 4H), 1.921.83 (m, 4H), 1.541.28 (m, 20H), 0.89 (t, J = 6.7 Hz, 6H).13 C NMR (75 MHz, CDCl3):δ 151.1, 146.7, 90.5, 69.3, 31.7, 29.2, 29.1, 28.5, 25.9, 22.6, 14.0. 4,7-Dibromo-5,6-bis(octyloxy)benzo[ c][1,2,5]oxadiazole (4, M1). AcOH (10 mL) and Br2(0.850 mL, 16.6 mmol) were added sequentially
to a solution of 5,6-bis(octyloxy)benzo[c][1,2,5]oxadiazole (3, 1.50 g, 4.00 mmol) in CH2Cl2(80 mL). The resulting mixture was stirred in the
dark for 3 days at room temperature and then poured into aqueous NaOH solution (10 g in 200 mL). The aqueous phase was extracted with CH2Cl2; the combined organic extracts were washed with brine and
concentrated under reduced pressure to afford a crude solid that was purified through column chromatography [SiO2, hexane/CH2Cl2, 9:1
(v/v)] to yield a white solid (2.2 g, 79%).1H NMR (300 MHz, CDCl3):
δ 4.13 (t, J = 9 Hz, 4H), 1.891.80 (m, 4H), 1.531.29 (m, 20H), 0.88 (t, J = 6.6 Hz, 6H).13C NMR (75 MHz, CDCl3):δ 155.6, 147.4, 99.5,
75.3, 31.7, 30.1, 29.3, 29.2, 25.8, 22.6, 14.0.
5,6-Bis(octyloxy)-4,7-di(thien-2-yl)benzo[c][1,2,5]oxadiazole(5). 2-Tributylstannylthiophene (994μL, 3.13 mmol) was added to a solution of 4,7-dibromo-5,6-bis(octyloxy)benzo[c][1,2,5]oxadiazole (4, 665 mg, 1.25 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3; 46 mg,
0.050 mmol), and tri-o-tolylphosphine (122 mg, 0.400 mmol) in dry toluene (10 mL) and then the reaction mixture was heated under reflux for 16 h under N2. The reaction mixture was concentrated directly
under vacuum. Dry column chromatography [SiO2, hexane/CHCl3, 10:1 (v/v)] afforded a yellow solid (470 mg, 70%).1H NMR (300 MHz,
CDCl3):δ 8.46 (d, J = 3.6 Hz, 2H), 7.50 (d, J = 6.3 Hz, 2H), 7.22 (t, J = 4.5 Hz, 2H), 4.14 (t, J = 7.2 Hz, 4H), 2.051.95 (m, 4H), 1.471.30 (m, 20H), 0.90 (t, J = 3.3 Hz, 6H).13C NMR (75 MHz, CDCl3):δ 151.6, 146.7, 132.8, 130.8, 128.0, 127.1, 113.0, 74.4, 31.8, 30.2, 29.5, 29.2, 25.8, 22.6, 14.0. 4,7-Bis(5-bromothien-2-yl)-5,6-bis(octyloxy)benzo[ c][1,2,5]oxadia-zole(M2). NBS (355 mg, 2.00 mmol) was added in one portion to a solution of 5,6-bis(octyloxy)-4,7-di(thien-2-yl)benzo[c][1,2,5]oxadia-zole (5, 540 mg, 1.00 mmol) in CHCl3(40 mL), and glacial AcOH
(40 mL) and then the mixture was stirred at room temperature for 20 h in the dark. The solution was concentrated directly onto Celite under vacuum. Dry column chromatography [SiO2, hexane/CHCl3, 9:1 (v/v)]
afforded an orange solid (800 mg, 92%).1H NMR (300 MHz, CDCl3):
δ 8.22 (d, J = 4.2 Hz, 2H), 7.15 (d, J = 4.5 Hz, 2H), 4.14 (t, J = 7.5 Hz, 4H), 2.041.94 (m, 4H), 1.471.30 (m, 20H), 0.90 (t, J = 2.4 Hz, 6H). 13 C NMR (75 MHz, CDCl3):δ 151.1, 146.1, 134.2, 131.1, 130.0, 116.3, 112.6, 74.7, 31.7, 30.1, 29.4, 29.2, 25.7, 22.6, 14.1. Anal. Calcd: C, 51.58; H, 5.48; N, 4.01. Found: C, 51.44; H, 5.47; N, 4.15.
General Procedure for Stille Polymerization. Alternating PolymerPTHBO. M1 (100 mg, 0.187 mmol), M3 (76.6 mg, 0.187 mmol), and tri(o-tolyl)phosphine (4.5 mg, 8.0 mol %) were dissolved in dry toluene (4 mL) and degassed for 15 min. Pd2(dba)3(3.4 mg,
2.0 mol %) was added under N2and then the reaction mixture was
heated at 110°C for 48 h. After cooling to room temperature, the solution was added dropwise into MeOH (100 mL). The crude polymer was collected, dissolved in CHCl3, and reprecipitated in MeOH. The
solid was washed with MeOH, acetone, and CHCl3 in a Soxhlet
apparatus. The CHCl3 solution was concentrated and then added
dropwise into MeOH. Finally, the polymer was collected and dried under vacuum to give PTHBO (70 mg, 80%).1H NMR (300 MHz, CDCl3): δ 8.688.57 (m, 2H), 4.414.27 (m, 4H), 2.631.21
(m, 24H), 0.97 (s, 6H). Anal. Calcd: C, 68.09; H, 8.35; N, 6.11. Found: C, 67.25; H, 8.18; N, 6.03.
Alternating PolymerPBTTBO. Using a polymerization procedure similar to that described above for PTHBO, a mixture of M2 (100 mg, 0.143 mmol) and M4 (102 mg, 0.143 mmol) in dry toluene (4 mL) was polymerized to give PBTTBO (93 mg, 70%).1H NMR (300 MHz, CDCl3):δ 8.578.02 (m, 4H), 7.076.57 (m, 2H), 3.96 (br, 4H), 2.45
(br, 4H), 1.560.96 (m, 48H), 0.89 (s, 12H). Anal. Calcd: C, 69.78; H, 8.24; N, 3.01. Found: C, 69.65; H, 8.17; N, 2.87.
Alternating Polymer PTTTBO. Using a polymerization procedure similar to that described above for PTHBO, a mixture of M2 (100 mg,
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0.143 mmol) and M5 (98.8 mg, 0.143 mmol) in dry toluene (4 mL) was polymerized to give PTTTBO (84 mg, 65%).1H NMR (300 MHz, CDCl3):δ 8.538.12 (m, 4H), 4.01 (br, 4H), 2.57 (br, 4H), 2.721.17
(m, 48H), 0.85 (s, 12H). Anal. Calcd: C, 69.13; H, 8.26; N, 3.10. Found: C, 67.85; H, 8.08; N, 2.95.
Measurements and Characterization.1H NMR spectra were
recorded using a Varian UNITY 300-MHz spectrometer. Thermogravi-metric analysis (TGA) was performed using a TA Instruments Q500; the thermal stabilities of the samples were determined under a N2
atmosphere by measuring their weight losses while heating at a rate of 20°C min1. Size exclusion chromatography (SEC) was performed using a Waters chromatography unit interfaced with a Waters 1515 differential refractometer; polystyrene was the standard; the tempera-ture of the system was set at 45°C and THF was the eluent. UVVis spectra of dilute samples in dichlorobenzene (DCB) solutions (1 105M) were recorded at ca. 25 and 60°C using a Hitachi U-4100 spectrophotometer. Solid films for UVVis spectroscopic analysis were obtained by spin-coating the polymer solutions onto a quartz substrate. Cyclic voltammetry (CV) of the polymer films was performed using a BAS 100 electrochemical analyzer operated at a scan rate of 50 mV s1; the solvent was anhydrous MeCN, containing 0.1 M tetrabutylammo-nium hexafluorophosphate ((TBA)PF6) as the supporting electrolyte.
The potentials were measured against a Ag/Ag+ (0.01 M AgNO3)
reference electrode; the ferrocene/ferrocenium ion (Fc/Fc+) pair was used as the internal standard (0.09 V). The onset potentials were determined from the intersection of two tangents drawn at the rising and background currents of the cyclic voltammograms. HOMO and LUMO energy levels were estimated relative to the energy level of the ferrocene reference (4.8 eV below vacuum level). X-ray diffraction patterns of the pristine polymer thin films were measured using a Bruker D8 high-resolution X-ray diffractometer operated in grazing incidence mode. Topographic and phase images of the polymer:PC61BM films
(surface area: 5 5 μm2) were obtained using a Digital Nanoscope III atomic force microscope operated in the tapping mode under ambient conditions. The thickness of the active layer of the device was measured using a Veeco Dektak 150 surface profiler.
Fabrication and Characterization of Photovoltaic Devices.
Indium tin oxide (ITO)coated glass substrates were cleaned stepwise in detergent, water, acetone, and isopropyl alcohol (ultrasonication; 20 min each) and then dried in an oven for 1 h; subsequently, the substrates were treated with UV ozone for 30 min prior to use. A thin
layer (ca. 20 nm) of poly(ethylenedioxythiophene):polystyrenesulfo-nate (PEDOT:PSS, Baytron P VP AI 4083) was spin-coated (5000 rpm) onto the ITO substrates. After baking at 140°C for 20 min in air, the substrates were transferred to a N2-filled glovebox. The polymer and
PC61BM were codissolved in DCB at various weight ratios, but with a
fixed total concentration (40 mg mL1). The blend solutions were stirred continuously for 12 h at 80°C and filtered through a PTFE filter (0.2 μm); the photoactive layers were obtained by spin-coating (6002000 rpm, 60 s) the blend solutions onto the ITO/PEDOT: PSS surfaces and then heating for 20 min at 100°C. The thicknesses of the photoactive layers were approximately 85105 nm. The devices were ready for measurement after thermal deposition (pressure: ca. 1 106mbar) of a 20 nm-thick film of Ca and then a 100 nm-thick Al film as the cathode. The effective layer area of one cell was 0.04 cm2. The current densityvoltage (JV) characteristics were measured using a Keithley 2400 source meter. The photocurrent was measured under simulated AM 1.5 G illumination at 100 mW cm2 using a Xe lampbased Newport 66902 150-W solar simulator. A calibrated Si photodiode with a KG-5 filter was employed to confirm the illumination intensity. External quantum efficiencies (EQEs) were measured using an SRF50 system (Optosolar, Germany). A calibrated monosilicon diode exhibiting a response at 300800 nm was used as a reference. For hole mobility measurements, hole-only devices were fabricated having the structure ITO/PEDOT:PSS/polymer/Au. The hole mobility was determined by fitting the dark JV curve into the space-charge-limited current (SCLC) method,17,37based on the equation
J ¼9 8ε0εrμh
V2 L3
whereε0is the permittivity of free space,εris the dielectric constant of
the material,μhis the hole mobility, V is the voltage drop across the
device, and L is the thickness of active layer.
’ RESULTS AND DISCUSSION
Synthesis and Characterization of the Polymers. Schemes 1 and 2 outline our general synthetic strategy for obtaining the monomers and the polymers. To ensure the good solubility of the BO derivative M1, we positioned two octyloxy chains on the BO ring. We synthesized M3, M4, and M5 using reported methods.13,32,36After Stille couplings using Pd2(dba)3
as catalyst in toluene at 110 °C for 48 h, we obtained the polymers PTHBO, PBTTBO, and PTTTBO in yields of 6580%. The highest concentration of the copolymers in tetrahydrofuran (THF), chloroform, chlorobenzene, and DCB
at room temperature is 25 mg mL1. We determined the weight-average molecular weights (Mw) of these polymers (Table 1)
through Size exclusion chromatography (SEC), against polystyr-ene standards, in THF as the eluent.
Thermal Stability.We used TGA to determine the thermal stability of the polymers (Figure 1). In air, the 5% weight-loss
temperatures (Td) of PTHBO, PBTTBO, and PTTTBO were
310, 312, and 315°C, respectively. Thus, they all exhibited good thermal stability against O2—an important characteristic for
device fabrication and application.
Optical Properties. We recorded the normalized optical UVVis absorption spectra of the polymers from their dilute DCB solutions at room temperature, hot DCB (60°C) and as spin-coated films on quartz substrates. Parts a and b of Figure 2 display the absorption spectra of PTHBO, PBTTBO, and
PTTTBO in DCB at room temperature and at hot DCB;
Table 2 summarizes the optical data, including the absorption peak wavelengths (λmax,abs), absorption edge wavelengths
(λedge,abs), and the optical band gap (Egopt). All of the absorption
spectra recorded from dilute DCB solutions feature two absorp-tion bands: one at 300450 nm, which we assign to localized ππ* transitions, and another broader band from 450 to 700 nm in the long wavelength region, corresponding to intramolecular charge transfer (ICT) between the acceptor (BO) and donor (thiophene derivatives) units. And while the absorption spectra blue shift by about 10, 16, and 38 nm for PTHBO, PBTTBO, and PTTTBO in hot DCB (60°C), respectively, as compared to that in DCB at room temperature, the interchain association band for PTHBO still remains at a higher relative intensity than that for PBTTBO and PTTTBO. This absorption behavior indi-cated that PTHBO aggregates in solution more strongly than
PBTTBOand PTTTBO. The absorption spectra of PBTTBO
and PTTTBO in hot DCB showed exactly the same peak was due to the similar molecular structure of 2,20-bithiophene (BT) to thieno[3,2-b]thiophene (TT). The absorption spectra Table 1. Molecular Weights, Thermal Properties, and Hole
Mobility of the Polymers
polymer Mwa(KDa) Mna(KDa) PDIa Tdb(°C)
mobilityc (cm2V1s1) PTHBO 52.8 35.2 1.5 310 9.7 104 PBTTBO 72.4 42.6 1.7 312 2.2 103 PTTTBO 74.7 41.5 1.8 315 1.2 103 aValues of M
n, Mw, and PDI of the polymers were determined through
GPC (polystyrene standards; THF).bThe 5% weight-loss temperatures in air.cThe measurement of hole mobility by the SCLC method.
Figure 1. TGA thermograms of the polymers PTHBO, PBTTBO, and PTTTBO, recorded at a heating rate of 20°C min1under a N2atmosphere.
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of the three polymers in the solid state were similar to their cor-responding solution spectra, with slight red-shifts (ca. 340 nm) of their absorption maxima, indicating that some intermolecular interactions existed in the solid state. In addition, PBTTBO and PTTTBO displayed a vibronic shoulders at 657 and 648 nm, respectively, implying an ordered arrangement in their solid films, with strongππ stacking between the polymeric backbones—a
feature that also appears in the spectra of regioregular poly-(3-hexylthiophene) (P3HT). The absorption edges for PTHBO, PBTTBO, and PTTTBO (Table 2) correspond to optical band gaps (Egopt) of 1.71, 1.7, and 1.72 eV, respectively.
Electrochemical Properties.The electrochemical properties of the thiophene derivative- benzooxadiazole based copolymers were examined by cyclic voltammetry (CV). Using this tech-nique the energy levels of the copolymer such as HOMO and LUMO can be determined. Figure 3 displays the electrochemical properties of the polymers as solid films; Table 3 summarizes the relevant data. Partially reversible n-doping/dedoping (reduction/ reoxidation) processes occurred for these polymers in the nega-tive potential range—except for PBTTBO, which underwent an irreversible reduction. In addition, reversible p-doping/dedoping (oxidation/rereduction) processes occurred in the positive po-tential range for each of these polymers. The onset oxidation potentials (Eonsetox , vs Ag/Ag+) for PTHBO, PBTTBO, and
PTTTBOwere 0.67, 0.33, and 0.48 V, respectively. The highest onset oxidation potential for PTHBO indicates that neighboring electron-deficient units do lead to better accepting properties, but the effect is small because of steric hindrance and the diluting segments between the electron donating/withdrawing moieties. In the reductive potential region, the onset reduction potentials (Eonset
red
) for PTHBO, PBTTBO, and PTTTBO were1.21, 1.8,
and1.74 V, respectively. On the basis of these onset potentials, we estimated the HOMO and LUMO energy levels according to the energy level of the ferrocene reference (4.8 eV below vacuum level).3840The HOMO energy levels of PTHBO, PBTTBO, and PTTTBOwere5.47, 5.13, and 5.28 eV, respectively, implying that they varied with respect to the modulated ICT strengths re-sulting from the presence of electron donors with various electron-donating abilities.4143 The LUMO energy levels of PTHBO, PBTTBO, and PTTTBO were all located within a reasonable range (from3.0 to 3.59 eV, Figure 4) and were significantly greater than that of PC61BM (ca. 4.1 eV); thus, we would expect
efficient charge transfer/dissociation to occur in their corresponding devices.4446In addition, the electrochemical band gaps (Egec) of
PTHBO, PBTTBO, and PTTTBO, estimated from the difference between the onset potentials for oxidation and reduction, were in the range 1.882.22 eV; i.e., they were slightly larger than the corresponding optical band gaps. This discrepancy between the electrochemical and optical band gaps presumably resulted from the exciton binding energies of the polymers and/or the interface barriers for charge injection.47
X-ray Diffraction Patterns. We confirmed the crystalline characteristic of thin films of these polymers from their grazing-incidence X-ray diffraction patterns (Figure 5). The (100), (200), and (300) diffraction peaks for PBTTBO appeared at 4.5°, 9°, and 13.5°, respectively, indicating a highly ordered structure with a d-spacing of 19.8 Å, ascribable to the interchain
Figure 2. UVvis absorption spectra of the polymers PTHBO, PBTTBO, and PTTTBO (a) in dilute DCB solutions (1 105M) at room temperature, (b) in hot DCB (60°C), and (c) as solid films.
Table 2. Optical properties of PTHBO, PBTTBO, and PTTTBO
λmax,abs(nm)
solution λonset(nm)
room temp heating film film Egopt(eV) PTHBO 605, 660 602, 650 605, 662 724 1.71
PBTTBO 574 558 600 726 1.70
separation of the alkyl side chains; we assign a broad feature at 24.4°, corresponding to a short distance of 3.6 Å, to facial ππ stacking of the polymeric backbones. The diffraction pattern of PTTTBO featured a sharp diffraction peak at 4.5°, which we assign to its (100) crystal plane (the d-spacing of 19.8 Å corresponds to the interchain separation defined by its alkyl side chains); we assign the broad reflection at 23° to its (010) crystal plane, corresponding to a distance of 3.8 Å, suggesting facial ππ stacking of the polymeric chains. In PTHBO, it only shows a broad reflection at 22.5° to its (010) crystal plane and correspond-ing to a distance of 3.9 Å .The crystalline characteristics of these polymers appeared to be favorable for charge transport within PSCs. Hole Mobility.Figure 6 displays the hole mobilities of the devices incorporating the pristine polymers and the Polymer/ PC61BM blends with the blend ratio of 1:1 (w/w). The hole
mobilities of the pristine PTHBO, PBTTBO, and PTTTBO
were 9.7 104, 2.2 103, and 1.2 103cm2 V1s1, respectively while that of PTHBO, PBTTBO, and PTTTBO blends were 1.1 104, 6.4 104, and 2.5 104cm2V1 s1, respectively. Thus, the hole mobility of the PBTTBO was greater than those of PTHBO and PTTTBO, presumably because of the greater crystallinity of PBTTBO.
Photovoltaic Properties.Next, we investigated the photo-voltaic properties of the polymers in BHJ solar cells having
the sandwich structure ITO/PEDOT:PSS/polymer:PC61BM
(1:1, w/w)/Ca/Al, with the photoactive layers having been spin-coated from DCB solutions of the polymer and PC61BM.
The optimized weight ratio for the polymer and PC61BM was
1:1. In this case, we added a small amount of 1,8-diiodooctane (DIO; 0.5%, by volume relative to DCB) to optimize the miscibility of the blends. Figure 7 presents the JV curves of these PSCs; Table 4 summarizes the data. The devices prepared
from polymer:PC61BM blends of PTHBO, PBTTBO, and
PTTTBO exhibited open-circuit voltages (Voc) of 1.02, 0.74,
and 0.87 V, respectively; each value is related to the difference between the HOMO energy level of the polymer and the LUMO
Figure 3. Cyclic voltammograms of the polymers PTHBO, PBTTBO, and PTTTBO as solidfilms.
Table 3. Electrochemical Properties of PTHBO, PBTTBO, and PTTTBO
Eonsetox (V) Eonsetred (V) HOMO (eV) LUMO (eV) Egec(eV)
PTHBO 0.67 1.21 5.47 3.59 1.88
PBTTBO 0.33 1.80 5.13 3.00 2.13
PTTTBO 0.48 1.74 5.28 3.06 2.22
Figure 4. Energy level diagrams for PTHBO, PBTTBO, and PTTTBO.
Figure 5. X-ray diffraction pattern of the pristine PTHBO, PBTTBO, and PTTTBOfilms.
Figure 6. Dark JV curves for the hole-dominated carrier devices incorporating the pristine polymers and the blendfilms prepared at a blend ratio of 1:1 (w/w) with 0.5 vol % of DIO.
ARTICLE energy level of PC61BM.48We suspect that the PBTTBO blend
provided the lowest value of Vocbecause of its relatively
higher-lying HOMO energy level. The short-circuit current densities
(Jsc) of the devices incorporating PTHBO, PBTTBO, and
PTTTBO were 8.3, 6.9, and 10.0 mA cm2, respectively.
Furthermore, when we incorporated DIO (0.5 vol %) into the
1:1 (w/w) polymer:PC61BM blends, the devices based on
PTHBO, PBTTBO, and PTTTBO exhibited slightly increased values of Jscof 9.0, 7.9, and 11.6 mA cm2, respectively, resulting
in increased PCEs. Figure 8 displays the EQE curves of the devices incorporating the polymer:PC61BM blends at weight
ratios of 1:1 and 0.5 vol % DIO as the additive. These devices exhibited significantly broad EQE responses that extended into the visible range. We attribute these EQE responses in the visi-ble region to the corresponding absorbances of the visi-blends, resulting from both the intrinsic absorptions of the polymers and the presence of PC61BM, which also absorbs significantly at
300400 nm. In contrast, these devices displayed relatively lower EQE responses at wavelengths of greater than 700 nm because of the moderate absorbances of the polymer blends in this range. The device based on the PTTTBO blend exhibited the highest EQE response among our studied systems, with a maximum of 60% at 580 nm, consistent with its higher photo-current. The theoretical short-circuit current densities obtained from integrating the EQE curves of the PTHBO, PBTTBO, and PTTTBOblends were 8.6, 7.5, and 11.1 mA cm2, values that agree reasonably with the measured (AM 1.5 G) values of Jscof
9.0, 7.9, and 11.6 mA cm2, respectively, with a discrepancy smaller than 5%.
The higher FF value of the device incorporating PBTTBO: PC61BM (1:1, w/w) active layer with 0.5 vol % DIO as the
additive is likely due to the higher hole mobility of the active layer, see Figure 6; the hole mobility of PBTTBO or
PBTTBO:PC61BM (1:1, w/w) is larger than that of PTHBO
and PTTTBO or PTHBO:PC61BM and PTTTBO:PC61BM.
Therefore, we attribute the enhanced FF to the increased hole mobility in the active layer, which is likely caused by the greater crystallinity in the PBTTBO active layer than in the
PTHBO and PTTTBO active layer.24 Notably, although
PBTTBO had the best crystallinity and hole mobility, it
provided the lowest value of Jscamong the three polymers.
We attribute this lower value of Jsc to the low absorption
coefficient (Figure 3c); consistently, the EQE curve also featured low EQE responses at 460680 nm. Thus, more of the available photons from the solar radiation could be absorbed by PTHBO and PTTTBO, leading to the higher photocurrents of their devices.
Moreover, when exploring the decisive factors affecting the efficiencies of PSCs we must consider not only the absorption and energy levels of polymers but also the surface morpho-logies of the polymer blends. Figure 9 displays the surface morphologies determined through AFM measurements. Sam-ples of the polymer:PC61BM blends were prepared using
pro-cedures identical to those used to fabricate the active layers of the devices. In each case, we observed a moderately homogeneous morphology of the polymer blends, except for the PTHBO blend, which displayed a coarse morphology. The root-mean-square roughness of PTHBO, PBTTBO, and PTTTBO were 9.3 nm, 3.8 and 3.1 nm, respectively (Figure 9ac). The greater phase segregation and rougher surfaces of PTHBO blends presumably arose because of poor miscibility with PC61BM, a
Figure 7. JV characteristics of PSCs incorporating polymer:PC61BM
blends and with 0.5 vol % DIO additive, each prepared at a blend ratio of 1:1 (w/w).
Table 4. Photovoltaic Properties of PSCs Incorporating BO-Based Polymers
polymer/PC61BM (1:1) (w/w) Voc(V) Jsc(mA cm2) FF (%) PCE (%) Rsh(Ω cm2) Rs(Ω cm2) thickness (nm) mobility (cm2V1s1)
PTHBO 1.02 8.3 51 4.2 445 15.2 82 PTHBOa 1.02 9.0 49 4.5 564 21.5 95 1.1 104 PBTTBO 0.74 6.9 72 3.7 1466 8.7 100 PBTTBOa 0.72 7.9 74 4.2 1285 8.1 102 6.4 104 PTTTBO 0.87 10.0 58 5.1 388 10.5 105 PTTTBOa 0.85 11.6 54 5.3 450 10.8 100 2.5 104
aProcessed with 0.5 vol % DIO.
Figure 8. EQE curves of PSCs incorporating polymer:PC61BM blends
result of the poor solubility of PTHBO compare with PBTTBO and PTTTBO. In contrast, Figure 9d to 9f display homogeneous morphology for the polymer/PC61BM blend films at weight
ratios of the 1:1 that were processed with 0.5 vol % DIO additive, indicating that the incorporation of 0.5 vol % DIO optimized the miscibility of polymer chains with PC61BM. The
root-mean-square roughness of PTHBO, PBTTBO, and PTTTBO were 8.8, 3.3, and 1.0 nm, respectively (Figure 9df). Through optimization of the blend morphology, such high values of Jsc
and PCE were also possible for the polymer:PC61BM blend at a
weight ratio of 1:1.
’ CONCLUSIONS
We have used Stille coupling polymerization to prepare a series of new crystalline, conjugated polymers—PTHBO, PBTTBO, and PTTTBO—featuring alternating thiophene-based building blocks and benzooxadiazole (BO) units in their backbones. These poly-mers possess excellent crystallinity, thermal stability and low-lying HOMO energy levels. These desirable properties make PTHBO, PBTTBO, and PTTTBO promising materials for solar cell applications. A device incorporating PTTTBO and PC61BM
(blend weight ratio, 1:1), with DIO (0.5 vol %) as an additive, exhibited a high value of Vocof 0.87 V and a PCE of 5.3%. Figure 9. Topographic AFM images of polymer:PC61BM (1:1, w/w) blends incorporating (a) PTHBO, (b) PBTTBO, and (c) PTTTBO and with 0.5
ARTICLE
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: khwei@mail.nctu.edu.tw.
’ ACKNOWLEDGMENT
We thank the National Science Council, Taiwan, forfinancial support (NSC 98-2120-M-009-006).
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