Solar Energy Materials & Solar Cells 109 (2013) 3339

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Solar Energy Materials & Solar Cells

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

Donor-acceptor small molecule with coplanar and rigid p-bridge for efcient organic solar cells
Liang-Chen Chi a, Hsiao-Fan Chen a, Wen-Yi Hung b,n, Yu-Hsiang Hsu b, Ping-Chi Feng b, Shu-Hua Chou a, Yi-Hung Liu a, Ken-Tsung Wong a,n
a b

Department of Chemistry, National Taiwan University, Taipei 106, Taiwan Institute of Optoelectronic Sciences, National Taiwan Ocean University, Keelung 202, Taiwan

a r t i c l e i n f o
Article history: Received 31 July 2012 Received in revised form 15 October 2012 Accepted 16 October 2012 Available online 16 November 2012 Keywords: DA small molecule Tandem photovoltaic cell Planar-mixed heterojunction

abstract
A novel donoracceptor (DA) donor molecule, 1, comprising of two di-p-tolylamino donors and a dicyanovinylene acceptor bridged by a planar and rigid uorene moiety has been synthesized and characterized. The molecular structure and crystal packing of 1 was characterized by single-crystal X-ray crystallography. Such molecular conguration endowed 1 with an efcient DA interaction, rendering an intense ICT absorption band for efciently light-harvesting and retain low-lying HOMO for generating sufcient open-circuit voltage (Voc). The vacuum-deposited hybrid planar-mixed heterojunction (PMHJ) photovoltaic devices utilizing 1 as donor and C70 as acceptor to achieve power conversion efciencies (PCEs) of 4.04 and 5.31% for the single- and tandem-cell photovoltaic devices under simulated AM 1.5 illumination (100 mW cm 2). & 2012 Elsevier B.V. All rights reserved.

1. Introduction Organic photovoltaics (OPVs) have been granted as potential energy resources because their unique features such as low-cost manufacturing, light-weight, and mechanical exibility.[15] Among various approaches, solution-processed bulk heterojunction (BHJ) solar cells based on low-band-gap p-conjugated polymers and soluble fullerene derivatives represented the most successful examples due to the formation of bicontinuous holeand electron-transport channels. The recent reports demonstrated that the power conversion efciencies (PCEs) for solutionprocessed polymer BHJ solar cells have been steadily achieved in the range of 68%.[617] Among them, a remarkable PCE of 8.37% has been reported for a PTB7-based device by incorporating a thin layer of alcohol/water-soluble polymer as a cathode interlayer.[18] More recently, small molecule organic solar cells (SMOSCs) can also deliver respectable PCEs, [1927] triggering the momentum for the rational design of small molecules with novel structural features used for solar cells. Through a rational molecular design of a donor molecule and a particular activelayer processing method, one can achieve a PCE of 7% for solutionprocessed SMOSCs.[28] Although solution-process is considered to be more cost-effective than that via vacuum deposition.

Corresponding author. Tel.: 886 2 24622192; fax: 886 2 24634360. E-mail addresses: wenhung@mail.ntou.edu.tw (W.-Y. Hung), kenwong@ntu.edu.tw (K.-T. Wong). 0927-0248/$ - see front matter & 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.solmat.2012.10.019

However, vacuum process can provide precise controlling parameters for device fabrication, giving device with sophisticated structure for efcient extraction of photocurrent. More importantly, vacuum deposition can pile two single-cells on top of each other to give tandem architecture, leading to superior PCE up to 10.7%.[29,30] Compared to the polymeric counterpart, small molecule exhibits advantages such as well-dened molecular structures, easier purication, and better batch-to-batch reproducibility, have successfully triggered the momentum for rational design of novel structural features useful for BHJ solar cells. Due to the remarkable electron afnities and high electron mobilities, [18,31] fullerenes and their derivatives are well-suited acceptors employed in SMOSCs. Therefore, most of endeavours are focused on the development of efcient donor materials with welltailored physical properties such as (i) extended absorption wavelength in visible region for better spectral overlap with solar spectrum; (ii) suitable energy level alignment to ensure efcient electron transfer process and maximum open-circuit voltage (Voc) and (iii) appropriate molecular planarity to accommodate just intermolecular pp stacking for better carrier conduction. Small molecule congured as donor(p-bridge)acceptor (DpA) with judicious selection of donor, acceptor, and p-bridge subunits is considered as a simple and effective molecular architecture to meet these criteria. Triphenylamine (TPA) and its derivatives have been widely employed as the efcient electron-donating and hole-transporting moieties, [3234] while various types of electronwithdrawing groups have been reported as good candidates for

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Br

Br

N H Pd(OAc)2 , PtBu3 , NaOtBu, Toluene, reflux 77 %

O 3

O 2

NC

CN
o

DMSO, 110 C 84 % NC 1 CN

Scheme 1. Synthesis and structure of donor molecule 1.

the electron-accepting subunits.[3542] In addition to the donor and acceptor subunits, the p-bridge unit is also crucial for tailoring the physical properties because it signicantly affects the way and extent of donoracceptor communication, namely the intramolecular charge transfer (ICT) efciency. The important issues such as small band-gap and energy levels matching to fullerenes of the donor materials used in SMOSCs can be manipulated by adjusting the degree of ICT. We envisioned that the desired physical properties of donor materials can be readily obtained by incorporating a short and rigid bridge unit, providing a simple strategy for giving efcient SMOSCs. In this contribution, we report a simple DA type small molecule 1 (Scheme 1), in which two electron-donating di-p-tolylamino groups and an electronwithdrawing dicyanovinylene are bridged by a coplanar uorene. It is worthy to note that the dicyanovinylene attached to the C9 of uorene gives uoren-9-ylidene malononitrile (FM) which has been reported as a good acceptor moiety. [43] Such molecular architecture reduces the donoracceptor distance and increases the molecular rigidity for bringing efcient ICT. The vacuumdeposited single-cell photovoltaic device employed 1 as donor and C70 as acceptor achieved a PCE of 4.04%. In addition, a tandemcell photovoltaic device with improved PCE up to 5.31% was achieved under simulated AM 1.5 illumination (100 mW cm 2).

570.2673; Anal. Calcd. C, 86.28; H, 6.00; N, 4.91, found C, 86.00; H, 6.02; N, 4.78. 3,6-bis(di-p-tolylamino)-uoren-9-ylidene malononitrile (1). A mixture of 2 (285 mg, 0.5 mmol) and malononitrile (66 mg, 1 mmol) was dissolved in DMSO (nitrogen bubbled, 10 mL) and stirred at 110 1C for 12 h. The reaction was cooled to room temperature and the resulting solid was ltered and successively washed with acetonitrile (20 mL) and hexane (30 mL) to afford pure 1 (260 mg, 84%) as a black solid. Mp 337 $ 338 1C; IR (KBr) n 3024, 2919, 2217, 1595, 1549, 1506, 1486, 1454, 1310, 1278, 1133, 1024, 863, 814, 719, 662; 1H NMR (CD2Cl2, 400 MHz) d 8.05 (d, J 8.4 Hz, 2H), 7.13 (d, J 8.4 Hz, 8H), 7.02 (d, J 8.4 Hz, 8H), 6.88 (d, J 2.0 Hz, 2H), 6.63 (dd, J 8.4, 2.0 Hz, 2H), 2.34 (s, 12H);13C NMR (CD2Cl2, 100 MHz) d 159.2, 153.6, 143.7, 135.6, 130.6, 127.9, 127.0, 126.6, 118.7, 115.9, 111.4, 21.3; MS (m/z, FAB ) 619 (1.37); HRMS (m/z, FAB ) Cacld for C44H34N4 618.2783, found 618.2784, Anal. Calcd. C, 85.41; H, 5.54; N, 9.05, found C, 85.45; H, 5.61; N, 9.00. 2.2. Physical property measurement Steady state spectroscopic measurements were conducted both in solution and solid lms prepared by vacuum (2 10 6 Torr) deposition on a quartz plate (1.6 1.0 cm). Absorption spectra were recorded with a U2800A spectrophotometer (Hitachi). Fluorescence spectra at 300 K and phosphorescent spectra at 77 K were measured on a Hitachi F-4500 spectrophotometer upon exciting at the absorption maxima. The experimental values of HOMO levels were determined with a Riken AC-2 photoemission spectrometer (PES), and those of LUMO levels were estimated by subtracting the optical energy gap from the measured HOMO. 2.3. Cyclic voltammetry The oxidation potential was determined by cyclic voltammetry (CV). 0.1 M nBu4ClO4 (TBAP) (reduction) in THF and 0.1 M nBu4PF6 (TBAPF6) (oxidation) in CH2Cl2 were used as supporting electrolytes. A glassy carbon electrode was used as the working electrode. Scan rate: 100 mV/s. The potential difference (DE 0.14 V) between the rst and second oxidations of 1 indicates that only limited resonance delocalization of the radical cation occurred as compared to that of 2,7-bis(diphenylamino)uorene derivative (DE 0.32 V).[44] The comproportionation constant (Kc), which is related to the degree of electronic interaction at the mixed-valence state [45,46], can be calculated to be

2. Experimental 2.1. Synthesis 3,6-bis(di-p-tolylamino)-9-uorenone (2). A mixture of 3,6dibromo-9-uorenone (3.38 g, 10 mmol), di-p-tolylamine (7.89 g, 40 mmol), palladium diacetate (120 mg, 0.5 mmol), sodium tertbutoxide (5.76 g, 60 mmol), and tri-tert-butylphosphine (0.05 M in toluene, 15 mL) was dissolved in toluene (150 mL) and reuxed for 48 h under argon. The reaction mixture was extracted with CH2Cl2 (200 mL 3). The organic layer was washed with brine then dried over MgSO4. The crude product was washed with methanol to afford pure 2 (4.68 g, 82%) as a dark red solid. Mp 149150 1C; IR (KBr) n 3025, 2919, 2857, 1694, 1596, 1508, 1483, 1325, 1273, 1243, 1107, 814, 679; 1H NMR (CD2Cl2, 400 MHz) d 7.35 (d, J 8.0 Hz, 2H), 7.11 (d, J 8.0 Hz, 8H), 7.016.99 (m, 8H), 6.93 (d, J 2.0 Hz, 2H), 6.65 (dd, J 8.0, 2.0 Hz, 2H), 2.32 (s, 12H); 13 C NMR (CD2Cl2, 100 MHz) d 190.5, 154.0, 145.5, 144.4, 134.8, 130.5, 128.0, 126.2, 125.0, 119.9, 112.2, 21.3; MS (m/z, FAB ) 571 (83.44); HRMS (m/z, FAB ) Cacld for C41H34N2O 570.2671, found

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233, which lies at the borderline between the class I and II systems according to the Robin-Day classication (the Kc for class II system is in a range of 100106).[47]

2.5. Fabrication and characterization of photovoltaic devices For device fabrication, all chemicals were puried through vacuum sublimation prior to use. The solar cells were fabricated through vacuum deposition of the materials at 10 6 Torr onto ITO glass substrates (15 O sq 1). The ITO surface was cleaned ultrasonically; i.e., with acetone, methanol, and deionized water in sequenceand nally with UV-ozone. The deposition rate of each s 1 and then capped with cathode organic material was ca. 12 A s 1) through shadow masking without breaking the (ca. 5 A vacuum. The effective photovoltaic area as dened by the geometrical overlap between the bottom ITO electrode and the top cathode was 1 mm2. After all of the fabricated devices were encapsulated in a glove box, the current-voltage (JV) characteristics were measured using a Keithley 2400 sourcemeter and an Oriel Xenon lamp (150 W) with an AM1.5 lter as the solar simulator under an ambient atmosphere. A calibrated photovoltaic reference cells was used to calibrate the light intensity to 100 mW cm 2. The spectral response was recorded under short circuit condition when devices were illuminated with a monochromatic light from a Xeon lamp.

2.4. Time-of-ight (TOF) mobility measurements Carrier-transport properties were studied in vapor-deposited glasses of 1 by the time-of-ight (TOF) transient photocurrent technique. The samples were prepared by vacuum deposition using the structure: ITO glass/ 1 (2.75 mm)/Ag (150 nm), and then placed inside a cryostat and kept under vacuum. The thickness of organic lm was monitored in-situ with a quartz sensor and calibrated by a thin lm thickness measurement (K-MAC ST2000). A pulsed nitrogen laser was used as the excitation light source through the transparent electrode (ITO) induced photogeneration of a thin sheet of excess carriers. Under an applied dc bias, the transient photocurrent was swept across the bulk of the organic lm toward the collection electrode (Ag), and then recorded with a digital storage oscilloscope. Depending on the polarity of the applied bias, selected carriers (holes or electrons) are swept across the sample with a transit time of tT. With the applied bias V and the sample thickness D, the applied electric eld E is V/D, and the carrier mobility is then given by m D/(tT E) D2/(VtT), in which the carrier transit time, tT, can be extracted from the intersection of two asymptotes to the tail and plateau sections in double-logarithmic plots.

3. Results and discussions Scheme 1 depicts the synthetic routes to the target donor compound 1. Pd-catalysed CN bond coupling of 2,7-dibromouorene (3), which was synthesized according to the literature procedure, [43] and di-p-tolylamine gave the uorenone (2) in 77% yield. The Knoevenagel condensation of 2 with malononitrile 1 gave the desired product with an isolated yield of 84%. The thermogravimetric analysis (TGA) of 1 gave a decomposition temperature (Td) (5% weight loss) of 357 1C, which is sufciently high to survive under high vacuum deposition. UV-Vis absorption spectra of 1 in solution and thin lm are depicted in Fig. 1. In CH2Cl2 solution, 1 showed strong absorption bands ranging from 400 to 700 nm with a highest molar absorptivity of 36400 M 1 cm 1 at 494 nm. FM derivatives exhibited signicant ICT character with the donor moieties appeared at 3,6-positions of FM. [43] Thus, the long wavelength absorption band (612 nm) of 1 can be unambiguously assigned to the ICT band between the amino-donor and the dicyanovinylene acceptor. The absorption of 1 was signicantly red-shifted as compared with that of the FM derivative with weaker donors, indicating our molecular design strategy combining the high rigidity of bridge and the close proximity of donor and acceptor can successfully extend the absorption toward longer wavelength. The thin lm absorption of 1 was slightly red-shifted and broadened, which is typically encountered in organic solid lms without signicant aggregation and/or intermolecular pp stacking. Density function theory (DFT) calculations revealed that the electron-donating

1.0 Film Sol.(DCM) 0.8 Absorbance (a.u.)

0.6

0.4

0.2

0.0 300

400

500 600 Wavelength (nm)

700

800

Fig. 1. Absorption spectra of 1 in CH2Cl2 and thin lm.

Fig. 2. Density function theory calculated HOMO and LUMO orbitals for 1. DFT calculations were performed at a B3LYP/6-31G (d) level for the geometry optimization.

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di-p-tolylamine and electron-withdrawing dicyanovinylene moieties explicitly contribute to HOMO and LUMO orbitals, respectively, whereas the central uorene moiety possesses both HOMO and LUMO distributions as shown in Fig. 2. The separated distributions of HOMO and LUMO orbitals are in line with the experimental observation of the ICT transitions. The electrochemical property of 1 was probed by cyclic voltammetry. Compound 1 exhibited two reversible oxidation potentials of 1.00 and 1.14 V and two reversible reduction potentials of 0.76 and 1.29 V vs. Ag/AgCl as shown in Fig. 3. We assigned two reduction sites as being located on the FM moiety, differenced by the coulombic repulsion exerted to the second reduction. For more practical use, we used photoelectron yield spectroscopy (Riken AC-2) to determine the HOMO energy level of 1 to be 5.25 eV. The low-lying HOMO allows 1 to potentially achieving a large Voc value as engaged with fullerenes in SMOSCs. The LUMO was estimated to be 3.44 eV from the HOMO and the optical band gaps (Eg) by using the equation LUMO HOMO Eg, where Eg is the onset wavelength of the absorption band.

30 20 10 Current (A) 0 -10 -20 -30 -40 1.5

The molecular structure of 1 was analysed by X-ray crystallography as shown in Figs. 4 and 5; the crystal data of was summarized in Table 1. Due to a large number of independent atoms in the asymmetric unit, the average R factor of 1 (0.0767) is slightly higher than the upper limit for small molecules (0.07, suggested by Acta Crystallographica).[48] The dicyanovinylene acceptor lies nearly at the same plane with coplanar uorene bridge (dihedral angle 0.981, the angle between the plane containing C14, C15, and C16 and plane containing C1, C2, and C13). The coplanar conguration facilitates the electronic coupling between the donor and the acceptor gives an evident ICT with bathochromic shifted absorption. It is noteworthy that the strong polar character and coplanar conformation of FM lead 1 to pack into an anti-parallel manner. In addition, the shortest point-topoint distance (C1-C1) between two neighbouring molecules was indicating substantial pp interactions. measured to be 3.42 A, The anti-parallel packing together with short intermolecular cofacial distance are expected to facilitate charge-hopping in the solid state.[49,50] The charge transport properties of the active materials play an important role in the OPV performance. Good carrier mobility ensures efcient exciton dissociation, charge transfer and reduces the charge recombination possibility, which eventually inuence the Jsc of OPV devices. We used time-of-ight (TOF) techniques to evaluate the associated carrier mobility. [51] Fig. 6(a) displays typical room-temperature TOF transient for 1 under an applied electric eld, for which we observed dispersive transient

1.0

0.5

0.0 -0.5 E (V vs. Ag/AgCl)

-1.0

-1.5

Fig. 3. Cyclic voltammograms of 1.

Fig. 5. X-ray-analysed molecular structure and crystal packing of 1.

Fig. 4. ORTEP diagram of 1. Thermal ellipsoids are drawn at 50% probability.

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Table 1 The crystal data of 1. 1 Empirical formula Formula weight Crystal dimensions (mm3) Crystal system Space group a (A) b (A) c (A) a (deg) b (deg) g (deg) 3 Cell volume (A) Z Density (calc) g/cm3 F(000) Temperature (K) Wavelength (A) No. of rens collected No. of indep rens (Rint) R(F), wR2 [I 4 2s(I)] R(F), wR2 (all data) C44H34N4 412.5 0.25 0.20 0.15 Monoclinic P2(1)/c 15.7363(3) 32.5548(8) 6.8187(2) 90 92.735(2) 90 3489.19(15) 6 1.178 1304 295(2) 1.54178 10507 6262(0.0267) 0.0511, 0.1436 0.0767, 0.1671

photocurrents for hole. Using double-logarithmic representations [inset of Fig. 6(a)], we extracted the hole-transit time (tT) from the intersections of the two asymptotes, which was used to determine the carrier mobilities. Fig. 6(b) shows the carrier mobilities of 1 plotted as a function of the square root of the applied electric eld, as well as the nearly universal PooleFrenkel relationship. The hole mobility of 1 is ranging from 3.8 10 6 to 8.5 10 5 cm2 V 1s 1 for elds varying from 2 105 to 5.3 105 V cm 1. To demonstrate the application of molecule 1 as an electron donor in organic solar cell, we used planar-mixed heterojunction (PMHJ) structure, [52] in which a mixed layer of donor and acceptor molecules sandwiched by the homogeneous layers of donor and acceptor. The single-stack PMHJ cells were fabricated by thermal evaporation congured as: ITO/MoO3 (30 nm)/1 (3 nm)/1:C60 or C70 (1: 1, 35 nm)/C60 or C70 (10 nm)/BCP (10 nm)/Ag (120 nm).[53] Fig. 7(a) shows the current density voltage (JV) characteristics of the PMHJ solar cells (device S-C60 and S-C70). The device S-C60 showed a PCE value of 3.12% with an open circuit voltage (Voc) of 0.97 V, a short circuit current density (Jsc) of 7.32 mA cm 2, and a ll factor (FF) of 0.44 under AM 1.5 G, 1 sun (100 mW cm 2) simulated solar illumination. For device S-C70, a higher PCE of 4.04% was achieved, and the Voc, Jsc and FF increased to 0.99 V, 7.64 mA cm 2, and 0.53, respectively. The photovoltaic characteristics of the devices are summarized in

200 hole Photocurrent (A) 160 Photocurrent (A) 100

10

Current Density (mA/cm2)

tT

120

-2

80

-4 Signal -6 C60 Dark Light C70 Dark Light 0.0 0.4 0.8 1.2 Voltage (V) 1.6 2.0 Tandem

0.1 40 10 100 Time (sec) 1000

0 0 200 400 Time (sec) 600 800

-8

1E-4 Hole mobility

60 50 40

(cm2/ V.s)

EQE (%)

1E-5

30 20 10 0

1E-6 400

500

600 E1/2 (V/cm)1/2

700

800

400

500 600 Wavelength (nm)

700

800

Fig. 6. (a) Representative TOF transient for 1 (hole, 2.75 mm thickness, E 2.67 105 V cm 1). Inset: double logarithmic plot. (b) Hole mobility vs. E1/2.

Fig. 7. (a) Current densityvoltage (JV) characteristics of 1:fullerene PMHJ solar cells with single- and tandem-stack structure under simulated AM 1.5 illumination of 100 mW cm 2 and (b) the spectral response of the single-stack PMHJ cells.

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Table 2 Summarized performances of single- and tandem-stack PMHJ cells. Device S-C60a S-C70a T-C60b T-C70b
a b

VOC/V 0.97 0.99 1.98 1.92

JSC/mA cm 2 7.32 7.64 4.90 5.00

FF 0.44 0.53 0.44 0.55

PCE/% 3.12 4.04 4.25 5.31

power conversion efciencies (PCE) of 4.04 and 5.31% for the single- and tandem-cell photovoltaic devices, respectively, under simulated AM 1.5 illumination (100 mW cm 2). We believe that the molecular design strategy disclosed here can trigger the innovative advance of small molecule based organic solar cells.

Acknowledgments
Single-cell. Tandem-cell.

Table 2. Generally, the Voc was found to depend strongly on the LUMO of the acceptor (C60 or C70) as well as on the HOMO of the donor (1). The LUMO value of C60 and C70 are almost at 3.9 eV. So, we observed the difference of Voc between S-C60 (0.97 V) and S-C70 (0.99 V) is only 0.02 V, which are close to each other. The higher PCE of S-C70 was ascribed to the wider absorption range of C70 relative to that of C60, which can be conrmed by the external quantum efciency (EQE) spectra of the PMHJ devices shown in Fig. 7(b). Device S-C70 exhibited superior broadband photoresponse spectrum covering 350600 nm. Nevertheless, both cells show a high and broad range of EQE response around 360 and 500 nm closely corresponding to the absorption spectrum of 1. One of the advantages imparted by vacuum-deposited organic solar cell is capable of fabricating tandem-cell using a serial connection of two individual cells, [3537] which can increase the open circuit voltage and achieve higher PCE. The tandem-cells were composed of two subcells by an inter-connecting layer (ICL) congured as: ITO/MoO3 (5 nm)/1 (3 nm)/1:C60 or C70 (20 nm)/ C60 or C70 (4 nm)/Bphen (8 nm)/Ag (0.5 nm)/HAT-CN (1.5 nm)/ MoO3 (5 nm)/1 (3 nm)/1:C60 or C70 (30 nm)/C60 or C70 (4 nm)/ Bphen (6 nm)/Al (100 nm). The individual cells were built up similarly to the PMHJ cells described above. A layer of Ag and a layer of 1, 4, 5, 8, 9, 11-hexaazatriphenylene hexacarbonitrile (HAT-CN) were introduce as inter-connecting layer (ICL).[54] Bathophenanthroline (Bphen) and Al were adopted as an exciton blocking layer and cathode, respectively. Fig. 6(a) shows the JV characteristics of tandem PMHJ solar cells incorporating C60 device (T-C60) and C70 device (T-C70). In 2-stack tandem system, the Voc can be equal to the sum of the open-circuit voltages of the individual cells. As expected, the tandem-cells showed nearly doubled Voc [T-C60 (1.98 V) and T-C70 (1.92 V) ] as compared with the single-stack cells and the difference is well within the normal range for error.The Jsc is reduced by less than 40% (4.9 and 5.0 mA cm 2) as compared to those of the single-cells (devices S-C60 and S-C70). Obviously, the trade-off between Voc and Jsc affords the tandem cells with signicantly higher PCEs of 4.25 and 5.31% in devices T-C60 and T-C70, respectively. In addition, high FFs of 0.44 and 0.55 are retained, indicating the photo-generation in the tandem sub-cells similar to the single-cells is relatively eld-independent. High Voc in the range of 1.92 V and high PCE value up to 5.31% were observed for tandem PMHJ cell (T-C70), which is comparable with those of state-of-art organic tandemcells based on small and polymeric molecules.[5457]

The authors gratefully acknowledge the nancial support from National Science Council of Taiwan (NSC 100-2112-M-019-002MY3, 101-2119-M-002-007-MY3).

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4. Conclusions In summary, we have demonstrated a simple but novel D-A type molecule (1), in which the donors (di-p-tolylamine) and the acceptor (dicyanovinylene) were bridged by a planar and rigid uorene moiety. Such molecular conguration endowed 1 with an efcient DA interaction, rendering an intense ICT absorption band for efciently harvesting the solar energy. The vacuumdeposited planar-mixed heterojunction (PMHJ) photovoltaic devices employing 1 as the donor and C70 as acceptor achieved

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