Near-infrared sensitive small molecule organic photovoltaic cells based on chloroaluminum phthalocyanine

Rhonda F. Bailey-Salzman, Barry P. Rand, and Stephen R. Forrest Citation: Appl. Phys. Lett. 91, 013508 (2007); doi: 10.1063/1.2752992 View online: http://dx.doi.org/10.1063/1.2752992 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v91/i1 Published by the American Institute of Physics.

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APPLIED PHYSICS LETTERS 91, 013508 2007

Near-infrared sensitive small molecule organic photovoltaic cells based on chloroaluminum phthalocyanine
Rhonda F. Bailey-Salzman and Barry P. Randa
Department of Electrical Engineering, Princeton University, Princeton, New Jersey 08544

Stephen R. Forrestb
Department of Electrical Engineering & Computer Science, University of Michigan, Ann Arbor, Michigan 48109; Department of Physics, University of Michigan, Ann Arbor, Michigan 48109; and Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109

Received 28 April 2007; accepted 4 June 2007; published online 5 July 2007 The use of chloroaluminum phthalocyanine ClAlPc as a donor and C60 as an acceptor in planar double heterojunction organic photovoltaic cells with response extending into the near infrared is demonstrated. X-ray diffraction indicates that under the conditions used in this study ClAlPc grows as an amorphous lm. Although the absorption and lm morphology show no dependence on growth rate, device performance is optimized at a growth rate of 0.5 / s, producing cells whose best performance gives an open circuit voltage of 0.68 0.01 V, a responsivity of 0.062 0.007 A / W, a ll factor of 0.50 0.04, and a power conversion efciency of 2.1 0.1% under simulated AM1.5G, 1 sun intensity illumination. This cell also displays low dark current under reverse bias, 2.4 108 A / cm2 at 1 V. 2007 American Institute of Physics. DOI: 10.1063/1.2752992 A major challenge preventing small molecule-based organic photovoltaic OPV cells from achieving high efciencies is the lack of materials absorbing in the infrared IR that allow for broad solar spectral coverage. Copper phthalocyanine CuPc, a commonly used donor material in OPVs,1 has an absorption spectrum that falls off at wavelengths of 700 nm. Recently, the use of tin phthalocyanine, which has absorption peaks at = 740 and = 860 nm, has resulted in an IR-sensitive OPV with a power conversion efciency of P = 1.0 0.1% under simulated AM1.5G, 1 sun illumination.2 Furthermore, polymers in bulk heterojunction OPVs have demonstrated P = 0.7% for materials with absorption to = 1000 nm,3 and P 3.2% for materials with absorption extending to 850 nm.4,5 An approach to increasing P of OPV cells involves nding materials combinations with a high open circuit voltage VOC. Recently, the donor molecule, boron subphthalocyanine chloride SubPc in combination with the acceptor C60 resulted in a cell with VOC = 0.98 V.6 This increase in VOC with respect to conventional CuPc-based cells results from the decrease of the highest occupied molecular orbital HOMO energy relative to vacuum of SubPc compared to that of CuPc.6,7 Here we demonstrate the use of chloroaluminum phthalocyanine ClAlPc as a donor in a planar double heterojunction OPV employing C60 as the acceptor. Under optimized conditions, these cells have VOC = 0.68 0.01 V, and a low dark current under reverse bias as compared to analogous CuPc/ C60 cells. Furthermore, ClAlPc has an absorption peak at = 755 nm, extending the cell photoresponse into the near IR. Previous work with ClAlPc has demonstrated a single heterojunction OPV with low efciency P 0.035% , partially attributed to the low purity materials used and hydraa

Present address: Polymer and Molecular Electronics, IMEC, Kapeldreef 75, B-3001 Leuven, Belgium. b Electronic mail: stevefor@umich.edu 0003-6951/2007/911/013508/3/$23.00

tion of ClAlPc.8 Those studies also showed morphology and crystallinity to be dependent on both growth conditions and substrate preparation and composition.9 Indeed, controlled growth has been exploited in Au/ ClAlPc/ n-Si cells to provide sensitization, and results in an enhanced VOC.10 Organic materials were puried by thermal gradient sublimation 3 cycles for C60 and 1 cycle for all other materials11 prior to being loaded in a thermal evaporation chamber with a base pressure of 5 107 Torr. Indium tin oxide ITO coated glass substrates with a sheet resistance of 15 / were solvent cleaned and ultraviolet ozone treated as described elsewhere.12 Absorption spectra were measured on 100 1000 thick lms thermally deposited on quartz substrates. Scanning electron microcopy SEM and atomic force microscopy AFM were used to image 200 thick lms thermally deposited at 0.1, 0.5, and 1.5 / s, on both ITO-coated glass and native oxide coated Si substrates. X-ray diffraction XRD data were collected in the BraggBrentano geometry for 1000 thick lms of ClAlPc thermally deposited at 1 / s on ITO-coated glass substrates. Ultraviolet photoelectron spectroscopy was used to determine the ionization potential of a ClAlPc lm grown under ultrahigh vacuum by organic molecular beam deposition11 at 1.5 / s on thermally deposited Ag on Si. The device structure grown by thermal evaporation consists of an ITO anode, a 200 thick lm of ClAlPc as donor, a 400 thick lm of C60 as acceptor, a 100 thick lm of bathocuproine BCP as the exciton blocking layer, and Ag as the cathode. A vacuum break to an inert nitrogen environment occurred between growth of the BCP layer and the Ag cathode to attach a shadow mask consisting of an array of 1 mm diameter openings. The cells were tested in air using a semiconductor parameter analyzer, and illuminated with an AM1.5G solar simulator using a 150 W xenon arc lamp. Neutral density lters were used to vary the intensity of the incident light.
2007 American Institute of Physics

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Bailey-Salzman, Rand, and Forrest

Appl. Phys. Lett. 91, 013508 2007

FIG. 2. Normalized absorption spectra for chloroaluminum phthalocyanine ClAlPc and copper phthalocyanine CuPc. ClAlPc has a peak at a wavelength of = 755 nm, redshifted from that of CuPc by approximately 135 nm. External quantum efciency is also shown for a planar double heterojunction organic photovoltaic cell with the structure indium tin oxide/ 200 ClAlPc/ 400 C60 / 100 bathocuproine/Ag in which the ClAlPc was grown at a rate of 0.5 / s.

FIG. 1. Color online a Molecular structural formula of chloroaluminum phthalocyanine ClAlPc. b Atomic force micrograph of a 200 thick lm of ClAlPc grown at 0.5 / s on an indium tin oxide substrate. Corresponding root mean square surface roughness was 53 . The vertical axis is on a scale of 40 nm/division and the horizontal axes are 0.2 m/division.

Figure 1a shows the molecular structural formula of ClAlPc. The Al atom, in the center of the phthalocyanine ring, is bonded to an out-of-plane Cl atom. This nonplanar structure inuences the molecular packing and hence lm morphology; a hypothesized slipped-deck stacking in a monoclinic lattice has been reported.8 Ultraviolet photoelectron spectroscopy was used to determine the ionization potential and hence the HOMO position relative to vacuum at 5.4 0.1 eV, compared to CuPc at 5.3 0.1 eV. XRD showed no ClAlPc diffraction peaks, indicating an amorphous lm. SEM and AFM images of lms grown at 0.1, 0.5, and 1.5 / s both on ITO-coated glass and on oxidized Si displayed similar morphologies and surface roughnesses. Figure 1b shows an AFM image of a 200 thick lm of ClAlPc on ITO-coated glass deposited at a rate of 0.5 / s. Measurements of ClAlPc lms deposited on ITO-coated glass substrates yield root mean square surface roughnesses of 57, 53, and 34 with respect to the increasing growth rate. Features of approximately 100 nm in diameter are observed on the lm surfaces in both SEM and AFM images. Figure 2 shows the absorption spectrum of ClAlPc along with that of CuPc for reference. The absorption for ClAlPc is signicantly redshifted, peaking at = 755 nm, compared to = 620 nm for CuPc. Although previous work with nonplanar IR absorbing materials has shown the absorption spectral shape depends on lm thickness due to molecular aggregation and dimer formation,2 we found no signicant peak shift or change in shape between thicknesses of 100 and 1000 . Absorption spectra were also measured for lms grown at rates varying from 0.1 to 1.5 / s, and again no signicant differences were observed. The external quantum efciency is also shown for an ITO/ 200 ClAlPc/ 400 C60 / 100 BCP/Ag OPV cell in Fig. 2. As expected from the absorption in the near IR, the photoresponse extends to = 800 nm. The C60 response is apparent at short wavelengths, peaking at = 480 nm. Current densityvoltage curves under various levels of illumination and in the dark are shown in Fig. 3a. The growth rate

of ClAlPc to achieve optimal device performance was 0.5 / s, although device parameters showed signicant runto-run variation, possibly due to impurities or materials degradation from heating during evaporation. Under simulated AM1.5G illumination at 119 mW/ cm2, the device open circuit voltage was VOC = 0.68 0.01 V, ll FF = 0.50 0.04, and responsivity JSC / P0 = 0.062 0.007 A / W, leading to P = 2.1 0.1%, uncorrected for spectral mismatch between the simulated spectrum and that of the sun.13,14 Figure 3b shows the dependence of P, VOC, and FF on incident optical power density P0. The data presented in Fig. 3 and Table I represent the best devices grown under the stated conditions. While these results were reproduced during initial studies, after several months of storing the source materials in air and under illumination, device performance noticeably degraded. The dark current under reverse bias is JD = 2.4 108 A / cm2 at 1 V. The exceptionally low JD results in

FIG. 3. a Current density vs voltage in the dark and under various simulated AM 1.5G illumination intensities for the structure indium tin oxide/ 200 chloroaluminum phthalocyanine ClAlPc / 400 C60 / 100 bathocuproine/Ag where the ClAlPc was grown at a rate of 0.5 / s. b Power conversion efciency P, open-circuit voltage VOC, and ll factor FF vs incident optical power density P0 for the same device as in a.

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Bailey-Salzman, Rand, and Forrest TABLE I. Organic photovoltaic cell results. ClAlPc growth rate /s 0.1 0.5 1.5 CuPc control
a

Appl. Phys. Lett. 91, 013508 2007

VOC Va 0.49 0.68 0.71 0.51

JSC / P0 A/W 0.064 0.062 0.050 0.060

FF 0.54 0.50 0.50 0.58

P %
1.7 0.1 2.1 0.1 1.8 0.1 1.8 0.1

Dark current at 1 V A / cm2 1.8 107 2.4 108 5.3 108 1.4 106

Open-circuit voltage, responsivity, ll factor, and power conversion efciency measured under simulated AM1.5G, 1 sun intensity illumination.

an increased VOC since VOC = kT / qlnIL / IS + 1 kT / qlnIL / IS, where k is the Boltzmann constant, T is the temperature, q is the elementary charge, IL is the photocurrent, and IS is the diode reverse saturation current.15 An increase in VOC is also expected due to the 0.1 0.1 eV larger interface energy gap dened as the difference in energy between the acceptor lowest unoccupied molecular orbital of the acceptor and the HOMO energy of the donor, as compared to that of the CuPc/ C60 system, consistent with previous analysis.6,7 Device performance was found to vary with the ClAlPc growth rate, although no signicant differences were observed in the lm microstructures or absorption. Table I summarizes the values of each performance parameter at each growth rate, as well as analogous CuPc-based devices. With increasing growth rate, VOC of the ClAlPc devices increases from 0.49 0.02 to 0.71 0.01 V. Conversely, JSC / P0 falls from 0.064 0.004 to 0.050 0.004 A / W, whereas FF remains relatively unchanged at 0.50 0.04. Finally, P rst increases and then falls off with rate, peaking at P = 2.1 0.1% at a growth rate of 0.5 / s. In contrast, the dark current at a reverse bias of 1 V decreases with increasing growth rate, with a minimum value of 2.4 108 A / cm2 at 0.5 / s, two orders of magnitude lower than for analogous CuPc-based devices. Note that the CuPc/ C60 device parameters of FF, JSC / P0, and P are signicantly lower than the highest reported values.1618 We have found the device performance to be strongly dependent on materials purity,12 which may account for reduced performance in this case. Nonetheless, VOC and P are signicantly increased relative to the CuPc control. Additionally, the FF and responsivities of both structures are similar, indicating that ClAlPc/ C60 elements are candidates for use in tandem cells19 to achieve spectral coverage into the IR. In conclusion, ClAlPc has been shown to be useful in OPV cells with response extending into the near IR. This material displays an enhanced VOC when compared to a CuPc/ C60 control device. The ionization potential of ClAlPc

is 0.1 eV larger than that of CuPc, thus leading to a concomitant increase in VOC.6,7 Finally, the low dark currents under reverse bias for these cells indicate that ClAlPc may also be useful in low noise photodetector applications. The authors gratefully acknowledge partial support of this work from the Air Force Ofce of Scientic Research Charles Lee, the Defense Advanced Research Project Agency Devendra Shenoy, and Global Photonic Energy Corporation.
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