Small molecular organic photovoltaic cells with exciton blocking layer at anode interface for improved device performance

Masaya Hirade and Chihaya Adachi Citation: Appl. Phys. Lett. 99, 153302 (2011); doi: 10.1063/1.3650472 View online: http://dx.doi.org/10.1063/1.3650472 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v99/i15 Published by the American Institute of Physics.

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APPLIED PHYSICS LETTERS 99, 153302 (2011)

Small molecular organic photovoltaic cells with exciton blocking layer at anode interface for improved device performance
Masaya Hirade1,2 and Chihaya Adachi1,2,3,a)
Center for Future Chemistry, Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395, Japan Life Beans Center Kyushu, Bio Electromechanical Autonomous Nano-Systems (BEANS) Laboratory, 744 Motooka, Nishi, Fukuoka 819-0395, Japan 3 I2CNER, Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395, Japan
2 1

(Received 16 August 2011; accepted 12 September 2011; published online 11 October 2011) We demonstrate enhanced power conversion efciency (gPCE) for small molecular-based organic photovoltaic cells with an exciton blocking layer (ExBL) at the anode/donor interface. Although poly(3,4-ethylenedioxythiophene):poly(4-styrene sulfonate) (PEDOT:PSS) lms are widely used as anodic buffer layers, they also act as exciton quenchers. To prevent exciton quenching, we introduced a tris[4-(5-phenyl thiophen-2-yl)phenyl]amine layer between the donor and the PEDOT:PSS layer and claried its effect. By a combination of dual ExBLs at both the anode and cathode sides, we achieved signicantly enhanced short circuit current and gPCE values; the highest C 2011 American Institute of gPCE 5.24% was obtained by optimizing the device parameters. V Physics. [doi:10.1063/1.3650472] To enhance the device performance of organic photovoltaic (OPV) cells, increasing exciton diffusion efciency to donor/acceptor (D/A) interfaces has been required because the exciton diffusion length of the organic thin lms is limited to typically less than 10 nm.1 Thus, various unique structures and materials such as bulk heterojunction structures,2 phosphorescent materials,3 and nanostructures4,5 have been widely considered for enhanced cell efciency. Further, prevention of exciton quenching at the metal electrodes is another important aspect, and recent conventional OPV cells have used an exciton blocking layer (ExBL) such as bathocuproine (BCP) at the acceptor/cathode interfaces to prevent exciton quenching.1 For the anode/donor interfaces, although many materials have been used as an anodic buffer layer, their function is mainly focused on suppression of the leakage current, leading to improved open-circuit voltage (VOC),6 and control of the morphology of the upper layers,7 providing a sensitization effect caused by energy transfer from the buffer layer to the donor layer.8 In particular, poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) is commonly used as an anodic buffer layer, providing a smooth anode surface and higher device stability compared to a bare indium-tin-oxide (ITO) electrode9 and reducing the leakage current.10 However, the PEDOT:PSS layer is a wellknown exciton quencher.11 Thus, the insertion of an ExBL at the PEDOT:PSS/donor interface should lead to greatly enhanced device performance. In previous studies, while some reports are suggestive for the possibility of the exciton blocking effect by anode buffer layers with rather wide energy gap layers, no clear conclusions based on experimental evidence have been reported.68,12 In this study, we introduced an ExBL into the anode/donor interface, achieved a signicant enhancement of the gPCE, and showed experimental evidence. We used tris[4-(5-phenylthiophen-2-yl)phenyl]amine13 (TPTPA, Fig. 1(a)) as exciton blocking layer and tetraphea)

Electronic mail: adachi@cstf.kyushu-u.ac.jp.

nyldibenzoperianthene14 (DBP, Fig. 1(a)) as donor layer. Because TPTPA has a wider energy gap of Eg $ 2.7 eV (estimated from the absorption edge) than that of DBP, for which Eg $ 1.9 eV (estimated from the absorption edge), it ensures exciton connement in the DBP layer by the TPTPA layer. Almost the same highest occupied molecular orbital (HOMO) levels were conrmed for both layers at around 5.4 eV by ultra-violet photoelectron spectroscopy (AC-2, Riken keiki Co.), providing no net energy barrier for hole collection into the anode through the TPTPA layer. Also, since the hole mobility of a TPTPA layer (lh $ 103102 cm2/Vs)13 is higher than that of a DBP layer (lh $ 104103 cm2/Vs),15 the hole transport process in the TPTPA layer is not a ratelimiting process. Thus, we can assume that TPTPA is suitable for the ExBL in a DBP based OPV cell. In this paper, we combine the merits of the semiconducting and optical characteristics of TPTPA and DBP to demonstrate signicantly improved OPV performance and clarify the exciton blocking effect of a TPTPA layer. First, we fabricated the devices, with a structure of ITO/ PEDOT:PSS/TPTPA (X nm)/DBP (Y nm)/C60 (50 nm)/BCP (10 nm)/Al (100 nm). We maintained the total thickness of the TPTPA/DBP stacked layer at 20 nm (X Y 20 nm). Figure 1(b) shows the J-V characteristics of the devices. The cell performances are summarized in Table I. The reference device, without the TPTPA layer, showed short circuit current density short circuit current density (JSC) of 5.61 6 0.08 mA/cm2, VOC of 0.92 6 0.01 V, ll factor (FF) of 0.72 6 0.01, and power conversion efciency (gPCE) of (3.88 6 0.06)%. The enhancements in JSC and gPCE were achieved by inserting a TPTPA layer, and the device performance was gradually enhanced with increasing thickness of the TPTPA layer. In particular, a device with a 10 nmthick TPTPA layer showed the maximum OPV performance with JSC 7.15 6 0.25 mA/cm2, VOC 0.93 6 0.01 V, FF 0.74 6 0.03, and gPCE (5.04 6 0.21)%, with the best gPCE value of 5.25%. The gPCE value was thus increased by about 1.2% compared to that of the reference device without
C 2011 American Institute of Physics V

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Appl. Phys. Lett. 99, 153302 (2011)

FIG. 1. (Color online) (a) Chemical structures of DBP and TPTPA; (b) J-V characteristics, and (c) action spectra of OPV cells with various TPTPA ExBL thicknesses. The solid line in (c) shows the absorption spectra of each active layer.

the TPTPA layer. On the other hand, the performance of the device decreased with a 15 nm-thick TPTPA layer. To discuss the details of these results, we compare the action spectra of the devices. Figure 1(c) shows the action spectra of the devices and the absorption spectra of each active material. From the action spectra, we see that the incident photon to current efciency (IPCE) from around 500600 nm, corresponding to the absorption region of the DBP layer, was enhanced by inserting the TPTPA layer, while the IPCE of this region in the device with the 15 nmthick TPTPA layer was greatly decreased in comparison to the other devices. In this case, the DBP layer was only 5 nm thick, and the absolute number of generated excitons was reduced, resulting in the low JSC. In the cases of the 10 and 15 nm-thick TPTPA layers, an increase in the IPCE at around 400 nm was observed, which is due to the sensitization effect caused by the TPTPA layer, i.e., part of the exciton generation in the TPTPA layer was transferred to the DBP layer.
TABLE I. OPV cell performance of ITO/PEDOT:PSS/TPTPA (X nm)/DBP (Y nm)/C60 (50 nm)/BCP (10 nm)/Al (100 nm) device. X Y (nm) (nm) JSC (mA/cm2) (1) (2) (3) (4) (4)a (5) (6) (7) (8) (9)
a

JSC and IPCE around the DBP absorption region were increased by the insertion of the TPTPA layer. Two possibilities must be considered for the origin of this enhancement. One is a morphological change in the DBP layer caused by inserting the TPTPA layer between the DBP and PEDOT:PSS layers, leading to enhanced absorbance in the DBP layer. The second is the exciton connement (blocking) effect of a TPTPA layer. First, we compared the correlation between the morphology and the absorbance of the DBP layers with and without a TPTPA layer. In the out-of-plane and in-plane x-ray diffraction (XRD) patterns of several organic layers, we obtained diffraction peaks for ITO, but no peaks for the organic layers.15 Also, inserting the TPTPA layer between the DBP and PEDOT:PSS layers had no inuence on the absorbance of the DBP layer.15 These results indicate that all of the organic layers have an amorphous phase, and no morphological changes or absorbance enhancements were produced by insertion of the TPTPA layer. Next, to estimate the exciton blocking effect of the TPTPA layer, we compared the photoluminescence (PL) intensity of the DBP layer in four lms composed of quartz/DBP (20 nm), quartz/PEDOT:PSS/DBP (20 nm), quartz/PEDOT: PSS/TPTPA (X nm)/DBP (20 nm), and quartz/TPTPA (X nm)/DBP (20 nm), with TPTPA thicknesses of X 1, 3, and 10 nm. Figures 2(a)2(c) show the PL spectra of these lms excited at 530 nm for the three different TPTPA thicknesses. Initially, with the insertion of a 1 nm-thick TPTPA layer, the PL intensity of the quartz/PEDOT:PSS/DBP lm was apparently lower than that of the quartz/DBP lm, indicating that the excitons in the DBP layer are partly quenched by the PEDOT:PSS layer. In the quartz/PEDOT:PSS/TPTPA/ DBP lm, on the other hand, the exciton quenching at the PEDOT:PSS layer was slightly suppressed, although the PL intensity was weaker than that of the quartz/TPTPA/DBP lm. Based on these results, we note that even the quartz substrate acts as an exciton quencher, although the origin of this action is unclear. Even with the insertion of a 3 nm-thick TPTPA layer, the PL intensity of the quartz/PEDOT:PSS/TPTPA/DBP was also weaker than that of the quartz/TPTPA/DBP lm, indicating that the exciton blocking effect of the 3 nm-thick TPTPA layer is still not enough. However, with the 10 nmthick TPTPA layer, we obtained almost the same PL

VOC (V) 0.92 6 0.01 0.93 6 0.01 0.93 6 0.01 0.93 6 0.01 0.94 0.93 6 0.01 0.93 6 0.01 0.93 6 0.01 0.93 6 0.01 0.93 6 0.01

FF 0.72 6 0.01 0.70 6 0.02 0.73 6 0.01 0.74 6 0.03 0.77 0.77 6 0.01 0.75 6 0.02 0.72 6 0.01 0.73 6 0.01 0.69 6 0.03

hPCE (%) 3.88 6 0.06 4.05 6 0.09 4.53 6 0.10 5.04 6 0.21 5.25 3.78 6 0.25 3.96 6 0.16 4.70 6 0.18 4.77 6 0.28 3.89 6 0.27

0 1 3 10 10 15 10 10 10 10

20 19 17 10 10 5 5 15 20 30

5.82 6 0.08 6.22 6 0.10 6.62 6 0.22 7.15 6 0.25 7.25 5.28 6 0.45 5.66 6 0.25 7.12 6 0.24 6.98 6 0.40 6.13 6 0.41

Best performance in this study.

FIG. 2. (Color online) PL spectra of the DBP layer in four samples of quartz/DBP (20 nm), quartz/PEDOT:PSS/DBP (20 nm), quartz/ PEDOT:PSS/TPTPA (X nm)/DBP (20 nm), and quartz/TPTPA (X nm)/DBP (20 nm), under excitation at 530 nm. The thicknesses of the TPTPA layers were (a) 1 nm, (b) 3 nm, and (c) 10 nm.

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153302-3

M. Hirade and C. Adachi

Appl. Phys. Lett. 99, 153302 (2011)

FIG. 3. (Color online) (a) J-V characteristics and (b) action spectra of OPV for various DBP layer thicknesses.

within 9 nm of the D/A interface mainly contribute to the photocurrent. A 10 nm-thick DBP layer is therefore enough for a donor layer. From these results, the exciton blocking effect of the TPTPA layer and the simultaneous exciton connement into the thin DBP layer are identied as key factors in the enhancement of the OPV performance. In this study, we prepared a small molecular OPV with an ExBL of TPTPA and conrmed the exciton blocking and connement effects. A 10 nm-thick TPTPA layer completely suppressed the exciton quenching and the combination of the TPTPA and DBP layers signicantly enhanced the device performance, resulting in a maximum gPCE of 5.25%. This is the one of the highest gPCE values ever reported for vacuum deposited OPV cells with a single cell structure and a planar heterojunction. We sincerely thank Dr. William Potscavage for fruitful discussion. This work was supported by a Grant-in-aid and a Fellowship from the Japan Society for the Promotion of Science (JSPS) and by the Global COE Program, Science for Future Molecular Systems from the Ministry of Education, Culture, Sports, Science and Technology of Japan, and the New Energy and Industrial Technology Development Organization (NEDO).

intensities for the DBP emission for the quartz/TPTPA/DBP lm and the quartz/PEDOT:PSS/TPTPA/DBP lm. We thus conclude that the 10 nm-thick TPTPA layer completely suppressed the exciton quenching caused by the PEDOT:PSS layer and the quartz substrate. To conrm the PL behavior, we checked the morphology of the TPTPA layer deposited on a PEDOT:PSS layer by measuring the AFM images of the layers. From the AFM images, we conrmed that the 10 nm-thick TPTPA layer completely covered the underlayer.15 Thus, a continuous TPTPA layer with 10 nm thickness is required for complete exciton connement. Next, we optimized the thickness of the donor layer. We xed the TPTPA thickness at 10 nm and varied the thickness of the DBP layer from 5 nm to 30 nm in a device structure of ITO/PEDOT:PSS/TPTPA(X 10 nm)/DBP(Y nm)/C60(50 nm)/BCP(10 nm)/Al(100 nm). Figures 3(a) and 3(b) show the J-V characteristics and the action spectra of the devices, and the cell performances were summarized in Table I. The highest device performance was obtained with the 10 nm-thick DBP layer. With the thinner DBP layers, JSC decreased, while the other performance levels were maintained. From the action spectra, we see that only the IPCE of the DBP absorption region was decreased, indicating that the DBP layer was too thin to completely absorb the irradiated light. However, with the thicker 30 nm DBP layer, JSC decreased. In the action spectra, the IPCE decreased across the entire range, indicating that the thick DBP layer increased the series resistance, leading to the decrease in JSC and FF. With a 1020 nm-thick DBP layer, almost the same high JSC level was obtained. To discuss the thickness dependence of the DBP layers, we measured the exciton diffusion length (LD) of a DBP layer using a PL quenching method.3 We estimate LD 9 6 3 nm,15 indicating that the excitons generated in the area

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