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phys. stat. sol. (b) 245, No. 9, 1834 1837 (2008) / DOI 10.1002/pssb.200779546

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Nanowirequantum-dotpolymer solar cell

A. Nadarajah, Robert C. Word, Kaitlyn VanSant, and R. Knenkamp*

basic solid state physics

Physics Department, Portland State University, 1719 SW 10th Avenue, Portland, OR 97201, USA Received 1 May 2008, revised 7 July 2008, accepted 8 July 2008 Published online 8 August 2008

Dedicated to Prof. Helmut Tributsch on the occasion of his 65th birthday

PACS 73.40.Lq, 81.05.Dz, 81.07.Pr, 84.60.Jt
*

Corresponding author: e-mail rkoe@pdx.edu

We report first results on a new solar cell structure which incorporates n-type ZnO nanowires, an undoped CdSe layer, obtained from quantum dot precursors, and a p-type polymer layer as the main components. In the fabrication process the quantum dot layer is converted to a conformal ~ 30 nm thick

polycrystalline film. The fabrication of the cell occurs in lab air at temperatures below 100 C. Several intermittent annealing steps raise the energy conversion efficiency to approximately 1%.

2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction In recent years a large number of novel device configurations for thin film solar cells have been explored including nano-structured dye-sensitized cells, inorganic nanowire cells, quantum dot cells, organic/inorganic hybrid cells and others. This broad exploratory development was largely triggered by the finding that nano-structuring can markedly improve the electronic transport and the optical absorption in solar cells. In addition nano-structuring also has the potential of facilitating fabrication processes and thereby reduce manufacturing cost. At this time the most successful example of a nanostructured solar cell is the dye-sensitized cell of ORegan and Grtzel [1] which is based on sensitization of a nanoporous wide-gap semiconductor with a tightly adsorbed molecular dye layer. The sensitization process itself had initially been explored by Tributsch and coworkers, who showed that high quantum efficiencies can be obtained in an electrochemical cell arrangement [2, 3]. The early work also clarified some of the unique properties of this type of sensitization process. The more recent success in demonstrating conversion efficiencies in the 10% range [1] has strongly stimulated further thinking on nanostructures in photovoltaics. Nanostructures are now being implemented into solar cells for many reasons and purposes. In this paper we describe a solar cell, which combines quantum dots, nanowires and polymers as the main com-

ponents. Very simple deposition processes are applied for this cell structure and these are optimized towards low cost fabrication. The cell structure is all-solid state, but it will be easy to adapt the preparation for flexible substrates. Figure 1 shows a schematic diagram of the device structure and SEM micrographs of its main components. Light absorption is provided by a thin layer obtained from quantum dots which conformally cover a vertically-oriented nanowire film. Depending on processing conditions, the layer can consist of loosely connected quantum dots or a continuous thin film of inter-connected quantum dots. The back contact is a polymeric hole conductor and an evaporated Au layer. The structure is designed to utilize the excellent electron transport properties of oriented crystalline nanowires [4] and the natural p-type conductance in polymers for the hole collection. The cell differs from similar previously reported cells, in which CdSe nanoparticles themselves establish the electron transport path to the front contact [5], or cells in which the absorption occurs in a polymer [6] or a dye layer [7], or cells in which the polymer is replaced by an inorganic compound [8], or cells in which the absorber is a true quantum dot layer [9]. In the cell discussed here a quantum dot layer is prepared in the initial deposition process, and is subsequently converted by reactive annealing into a conformal and uniform thin film around the nanowires. It will be shown that this conversion
2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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phys. stat. sol. (b) 245, No. 9 (2008) 1835

Figure 1 (online colour at: www.pss-b.com) a) Schematic diagram of the solar cell structure; b) ZnO nanowire films used as n-type conductor grown on F-doped SnO2; c) quantum dot layer on ZnO nanowires after anneal; d) encapsulation in MEH-PPV.

improves the overall performance of the solar cell considerably. When the thickness of the converted film is ~30 nm, satisfactory light absorption for wavelengths <750 nm is obtained and external quantum efficiencies up to 40% can be reached over a substantial portion of the visible spectrum. 2 Experimental ZnO nanowires were grown on fluorine-doped SnO2 substrates in electrodeposition at 80 C using a standard 3-electrode electrochemical cell with Pt counter and Ag/AgCl reference electrodes. Before deposition the substrates were cleaned ultrasonically in acetone and methanol with subsequent rinsing in HNO3 and distilled H2O. The deposition used aqueous solutions of 0.1 M KCl and 0.3 mM ZnCl2 saturated with O2 gas. Al doping was provided by addition of AlCl3 to the solution. More details on the deposition process are given in Ref. [10]. The nanowires are typically 12 m long, 100200 nm in diameter and their orientation is within 30 from the substrate normal. CdSe quantum dots capped with octadecyl amine ligands were obtained commercially and dissolved in toluene at a concentration of 2 g/l. The quantum dot solution is drop-coated in a sequence of 24 depositions, and annealed in a mixture of air and CdCl2 vapor at 380 C for durations from 30 min to 30 h. A thin MEHPPV (poly[2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene vinylene]) layer and an evaporated Au contact are deposited on top of the CdSe/ZnO structure to provide a p-type contact. The completed devices are annealed in vacuum for
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58 h at 125 C. As an alternative to the MEH-PPV, P3HT (poly(3-hexylthiophene)) was used in later devices. The annealing occurs in lab air in the presence of CdCl2 crystallites. The annealing process liberates the CdSe quantum dots from their organic ligands and promotes connectivity and grain growth in the particle layer. Depending on the duration of the anneal process the morphology of the quantum dot layer can be changed from that of a loosely connected particle film to a continuous polycrystalline film with large grain size. Transmission electron (TE) microscopy shows that the polycrystalline films are nicely conformal to the nanowires. Figure 2 shows some TE micrographs of the morphology change. Parts a) and b) show crystalline quantum dots of ~7 nm average diameter, while c) and d) display the converted polycrystalline film after 2 h anneal at 380 C. 3 Performance results and discussion Figure 3 shows plots of the external quantum efficiency and its improvement with increasing anneal time. Without anneal, i.e. with the as-deposited quantum dot layer, the device shows a very small quantum efficiency (<1%). The photoresponse onset occurs at approximately 600 nm corresponding to a photon energy of ~2 eV, which lies well above the energy gap of bulk CdSe (1.75 eV). Quantum confinement effects [11] and deviations from stoichiometry in the quantum dots are the likely reasons for the blue-shifted onset. A more detailed analysis confirms that the blue-shift becomes larger with decreasing quantum dot size. However, the ob 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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A. Nadarajah et al.: Nanowirequantum-dotpolymer solar cell

15 nm a)

5 nm
2 nm

50 nm
50 nm

2 nm

5 nm

b)

c)

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Figure 2 a) CdSe quantum dot layer after deposition; single quantum dots are visible in the TEM micrograph. b) High-resolution micrograph showing crystallinity of single quantum dots with average size of ~ 7 nm, corresponding to their size in the colloidal solution. c) Conformal coverage of quantum dot layer on ZnO after annealing at 380 C in air/CdCl2. d) High-resolution micrograph after 24 h anneal. The crystallite size is now ~ 30 nm.

served shift appears to be larger than what is expected from confinement effects alone, indicating that chemical effects may also contribute. With annealing of the glass/SnO2/ZnO/CdSe structure, the quantum efficiency improves significantly, as shown in Fig. 3. The annealing is carried out in CdCl2 vapor and air at 380 C before the back contact is deposited. Typically after 2 h anneal the quantum efficiency is increased by more than tenfold. If we define the photoresponse onset as the extrapolation of the steepest decent tangent to zero, the onset lies at ~750 nm after 2 h anneal. This wavelength corresponds to ~1.65 eV, an energy slightly below the bulk energy gap of CdSe. This strong shift away from the 2 eV onset for the as-deposited quantum dot layer is quite consistent with the structural changes observed in the electron micrographs: The annealing produces a continuous poly-

crystalline film in which carrier confinement effects are no longer active and in which the stoichiometry is better adjusted. The shift below the bulk bandgap value is likely due to a comparably large residual defect density related to grain boundaries and interface strain. Such defects often give rise to tail states and bandgap narrowing [12]. As the

a)

b) Figure 4 Solar cell characteristics: a) short-circuit current density vs. light intensity exhibiting linear behavior; b) open-circuit voltage vs. light intensity showing logarithmic behavior as expected from simple diode theory. Recent experiments show that the functional dependencies shown in a) and b) extend into the region of 85 mW/cm2.
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Wavelength (nm)

Figure 3 (online colour at: www.pss-b.com) Improvement of solar cell performance with increasing anneal time for annealing at 380 C in air/CdCl2.
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phys. stat. sol. (b) 245, No. 9 (2008) 1837

Figure 5 (online colour at: www.pss-b.com) Current voltage characteristics in optimized cells with the structure F-doped SnO2/ZnO/CdSe/MEH-PPV.

4 Conclusions We have presented first results on a novel hetero-junction solar cell prepared from ZnO and CdSe nanostructures. Free-standing ZnO nanowires are used to provide an enlarged substrate area for a very thin absorber film and to improve the electron transport from the absorber region towards the SnO2 front contact. The absorber itself is prepared as a nano-particle layer from CdSe quantum dots, which are converted to a continuous polycrystalline film by annealing. The back contact is provided by a polymer/metal contact. MEH-PPV as well as P3HT have been explored for this contact, best results were obtained with P3HT. All deposition processes are carried out in lab air and at temperatures below 100 C, but a number of intermittent annealing steps at temperatures between 100 C and 300 C are needed to raise the conversion efficiency towards the 1% regime. In many ways this work follows concepts of the extremely-thin-absorber solar cell (eta-cell) introduced earlier [13].
Acknowledgment Part of this work was supported by the Oregon Nano- and Microtechnologies Institute.

annealing time is further increased, the quantum efficiency continues to rise, the spectrum onset becomes progressively steeper, and the onset position moves up in energy towards the CdSe bandgap value. For an anneal time of 24 h the onset lies at ~1.70 eV and the quantum efficiency is maximized. Micrographs c) and d) in Fig. 2 correspond to this state of CdSe film. Further anneal leads to a deterioration of the quantum efficiency. In the completed and optimized device structure the short-circuit current is proportional to the light intensity and the open-circuit voltage has a logarithmic dependence on intensity, as shown in Fig. 4. This behavior is as expected from simple diode theory, and is consistent with the notion that the various hetero-junctions in the structure have the same direction of rectification. This conclusion is also supported by the dark rectification ratio which is close to 103 at 0.5 V. Under 85 mW white light from an unfiltered quartz-halogen lamp the output power is 0.8 mW corresponding to an energy conversion efficiency of 0.9% as shown in Fig. 5. In more recent work we have replaced the MEH-PPV with a thin P3HT polymer layer. P3HT is known to have a higher conductivity and appears to be more stable against oxidation. With a P3HT/Au back contact the energy conversion efficiencies under the same illumination conditions are of the order of 1.5%.

References
[1] B. ORegan and M. Grtzel, Nature 353, 737 (1991). [2] H. Tributsch, Photochem. Photobiol. 16, 261 (1972). [3] R. Memming and H. Tributsch, J. Phys. Chem. 76, 43 (1971). [4] R. Knenkamp, K. Boedecker, M. Poschenrieder, F. Zenia, C. Levi-Clement, and S. Wagner, Appl. Phys. Lett. 77, 2575 (2000). [5] W. U. Huynh, J. J. Dittmer, W. C. Libby, G. L. Whiting, and A. P. Alivisatos, Adv. Funct. Mater. 13, 73 (2003). [6] D. C. Olson, J. Piris, R. T. Collins, S. E. Shaheen, and D. S. Ginley, Thin Solid Films 496, 26 (2006). [7] M. Law, L. E. Greene, J. C. Johnson, R. Saykally, and P. Yang, Nature Mater. 4, 455 (2005). [8] C. Lvy-Clment, R. Tena-Zaera, M. A. Ryan, A. Katty, and G. Hodes, Adv. Mater. 17, 1512 (2005). [9] K. S. Leschkies, R. Divakar, J. Basu, E. Enache-Pommer, J. E. Boercker, C. Barry Carter, U. R. Kortshagen, D. J. Norris, and E. S. Aydil, Nano Lett. 7, 1793 (2007). [10] R. Knenkamp, R. Word, and M. Godinez, Nano Lett. 5, 2005 (2005). [11] Q. Dai, Y. Song, D. Li, H. Chen, S. Kan, B. Zou, Y. Wang, Y. Deng, Y. Hou, S. Yu, L. Chen, B. Liu, and G. Zou, Chem. Phys. Lett. 439, 65 (2007). [12] See for example: R. A. Street, Hydrogenated Amorphous Silicon (Cambridge University Press, 1991). [13] K. Ernst, A. Belaidi, and R. Knenkamp, Semicond. Sci. Technol. 18, 475 (2003).

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