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Solar Energy 85 (2011) 17801786 www.elsevier.com/locate/solener

Large photocurrent generation of an ITO electrode modied with a red copper(II) complex
Lin-Ying Li a, Meng-Yun Xu a, Xi Chen a, Qian-Jin Zhang b, Ke-Zhi Wang a,
b a College of Chemistry, Beijing Normal University, Beijing 100875, China College of Life Sciences, Beijing Normal University, Beijing 100875, China

Received 17 November 2010; received in revised form 19 March 2011; accepted 18 April 2011 Available online 14 May 2011 Communicated by: Associate Editor Sam-Shajin Sun

Abstract A lm of copper complex [CuL](NO3)2 (L = 2,3,8,9-tetraphenyl-1,4,7,10-tetraazacyclododeca-1,3,7,9-tetraene) formed on indiumtin oxide (ITO) coated glass by the solvent evaporation of the acetonitrile solution of the complex onto the ITO substrate, was characterized by ultraviolet-visible absorption spectroscopy, cyclic voltammetry, scanning electron microscopy, and photoelectrochemistry. The photoelectrochemical cell by using [CuL](NO3)2 modied ITO, a saturated calomel electrode, and platinum wire as working, reference and counter electrodes respectively in 1 M Na2SO4, was found to exhibit a large prompt and reproducible cathodic photocurrent density of 71 lA/cm2 under white light irradiation of 70 mW/cm2 at an applied potential of 0.4 V, and an incident photon to current eciency (IPCE) of 1.1% at k = 660 nm. This Cu(II) complex photosensitizer has advantages of simple synthesis, low-cost, environmentally benign and good photoelectrochemical performance. 2011 Elsevier Ltd. All rights reserved.
Keywords: Copper; Shi base; Photoelectrochemical property; Photocurrent

1. Introduction Fossil fuels as a nite resource are overwhelmingly believed to lead to climate-altering accumulation of CO2 in the atmosphere. In this context, low-cost and ecient conversion of solar energy have emerged as a crucial goal, as solar energy is the only renewable energy source with the proven capacity to meet the worlds increasing energy needs (Robertson, 2008). Since high-eciency conversion of solar radiation to electrical power has been achieved by Gra tzel and coworkers, who proposed a very ecient solar cell with TiO2 and ruthenium complexes, dye-sensitized solar cells (DSSCs) have been under active investigation as alternatives to silicon-based photovoltaic devices
Corresponding author. Tel./fax: +86 10 58805476.

E-mail address: kzwang@bnu.edu.cn (K.-Z. Wang). 0038-092X/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.solener.2011.04.018

for solar energy utilization (Anandan et al., 2005; Lee et al., 2009). Over the last four decades, Ru(II) polypyridyl complexes have attracted tremendous interest as photosensitizers for conversions of solar energy into chemical or electrical energy (Anandan et al., 2005; Lee et al., 2009). However, there are some potential drawbacks of noble metal-based devices, including high costs and environmental concerns. It is therefore worthwhile to develop alternatives that overcome these drawbacks. In this regard, one could be eager for other families of metal complexes that are comparable to, or even surpass Ru(II)polypyridyl complexes. Since copper(I) complexes with 2,9-disubstituted-1,10-phenanthroline ligands were recognized to possess similar photophysical properties to archetypal [Ru(bpy)3]2+ (bpy = 2,2-bipyridine) salts (Vante et al., 1983), these copper(I) complexes of bpy and 1,10-phenanthroline derivatives have attracted attention as

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sensitizers for solar cells (Alonso-Vante et al., 1994; Sakaki et al., 2002; Bessho et al., 2008), and related research advances have been given in two elegant recent reviews (Robertson, 2008; Ardo and Meyer, 2009). In addition, Cu(II) complexes have also played important roles as both sensitizers and electron-transfer mediators in photoelectrochemical solar cells. The copper(II) complexes of [(-)-sparteine-N,N0 ](maleonitriledithiolato-S,S0 )copper ([Cu(SP) (mmt)])0/, bis(2,9-dimethy-1,10-phenanthroline)copper ([Cu(dmp)2]2+/+), and bis(1,10-phenanthroline)copper ([Cu (phen)2]2+/+), and Ru dye cis-dithiocyanato-N,N0 -bis(4-carboxylato-4-tetrabutylammonoiumcarboxylate-2,20 -bipyridine)ruthenium(II) (N719) were reported as electron-transfer mediators and sensitizer in dye-sensitized solar cells, achieving light power conversion eciencies of 0.1%, 1.4%, and 1.3%, respectively (Hattori et al., 2005). Sing and coworkers reported copper(II) phthalocyanine-based solid-state organic hetero-junction solar cell of indiumtin oxide (ITO)/ poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid/ copper phthalocyanine/3,4,9,10-perylenetetracarboxylic bisbenzimidazole/aluminum, obtaining an open-circuit photovoltage of 1.15 V and a short-circuit photocurrent density of 0.125 mA/cm2 (Singh et al., 2006). Valli et al. reported copper(II) tetrakis-(isopropoxy-carbonyl)phthalocyanine modied TiO2 nanocrystal hybrid heterojunction device with a low photocurrent density of $15 nA/cm2 (Ingrosso et al., 2009). Zakeeruddin and Gratzel et al. reported a Cu(II) complex 2,7,12,17-tetrapropionic acid of 3,8,13,18-tetramethyl-21H,23Hporphyrin sensitized TiO2 nanocrystalline solar cell with a power conversion eciency of 3.8% (Alibabaei et al., 2010). By coordination of copper(II)-2,20 :60 ,200 -terpyridine (CuIItpy) with oxidized carbon nanohorns (CNHsCOOH), Tagmatarchis and Ito et al. prepared CNHs-COO-CuIItpy metallo-nanocomplexes, and conrmed intercomponent photoinduced charge separation with the aid of an electron mediator of hexyl-viologen dication (Rotas et al., 2008). Zhong et al. reported polythiophene carrying 8-hydroxyquinoline complex with Cu(II) as a dye sensitizer in dye-sensitized solar cell, giving an open-circuit photovoltage of 0.63 V, a short-circuit photocurrent density of 1.872 mA/cm2, and a power conversion eciency of 0.78% (Xiao et al., 2010). Although the photoelectric conversion eciencies so far reported for Cu(I) and Cu(II) complexes remained lower than those for Ru(II) dyes, the metal copper has advantages of the natural resource abundance of copper ore, and environmentally friendly over other metals. To the best of our knowledge, copper complexes reported in literature as photoelectrochemical solar cell sensitizers or electron-transfer mediators have been very rare compared to Ru(II) sensitizers (Robertson, 2008; Ardo and Meyer, 2009). Here we report a red 12-membered tetra-imine macrocycle Cu(II) complex as a good photoelectrochemical sensitizer for ITO electrode with a large cathodic photocurrent density of 71 lA/cm2 under white light irradiation of 70 mW/cm2, and an incident photon to current eciency (IPCE) of 1.1% at k = 660 nm.

2. Experimental 2.1. Materials [CuL](NO3)2 (L = 2,3,8,9-tetraphenyl-1,4,7,10-tetraazacyclododeca-1,3,7,9-tetraene) was prepared according to the literature (Bhoon and Singh, 1981), and its molecular structure is shown in Fig. 1. The other reagents were commercially available, and were used without further purication. 2.2. Substrates Indiumtin oxide (ITO) coated glass substrates were washed by ultrasonication in detergent and deionized water for 10 min each, and were then put into a mixture consisting of 25% NH3H2O, 30% H2O2, and deionized water (v/ v/v, 1:1:5) at 70 C for 20 min, followed by rinsing with copious deionized water and then vacuum dried. 2.3. Preparation of the lm electrode [CuL](NO3)2/ITO The ITO sheets precleaned as described above, were covered with the acetontirile solutions of the copper complex with varied concentrations from 4 to 20 mM by dropping pipettes, and were then vacuum dried at 55 C for 30 h. The thus obtained lm electrodes were soaked in 1 M Na2SO4 aqueous solutions and were subjected to white light irradiation (70 mW/cm2) for 5 min prior to UVvisible (UVvis) spectroscopy, scanning electron microscopy, cyclic voltammetry and photoelectrochemical measurements. 2.4. Instrumentation Ultraviolet-vis spectra of [CuL](NO3)2 lms on ITO were measured on a Cintra 10 e UVVis spectrophotometer with a blank ITO as the reference. All of the electrochemical and photoelectrochemical experiments were performed on a CHI-601 voltammetric analyzer in a three-electrode conventional cell at the ambient laboratory temperature (22 2 C) in 1 M Na2SO4 aqueous solution, equipped with an ITO glass modied with the copper complex, a platinum wire and a saturated calomel electrode (SCE) as working, counter and reference electrodes, respectively. Throughout the experiments, an IR light lter was

Fig. 1. Molecular structure of [CuL](NO3)2.

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tted with a 500 W xenon lamp system, in order to protect electrodes from heating. The white light intensities were measured with a Model ST-900M Photometer (Photoelectric Instrument Factory of Beijing Normal University). To acquire the photocurrent action spectrum, a monochromatic light was obtained from a 500 W xenon lamp (Changtuo Photoelectronic Technology Ltd., Beijing, PR China) tted with a certain additional bandpass lter with the spectral width of 5 nm. The monochromatic light intensities were measured with a light gauge radiometer, which is corrected by standard silicon cells (FZ-A, Photoelectric Instrument Factory of Beijing Normal University). Morphology and composition analysis of a bare ITO glass and [CuL](NO3)2 lms on ITO glass were performed on a Hitachi X-650 scanning electron microscope with an EDAX-9100 energy dispersive spectrum device, using an accelerating voltage of 10 kV. 3. Results and discussion 3.1. Scanning electron microscopy The surface morphology and composition analysis of the lms were characterized by scanning electron microscope (SEM), and the SEM images are shown in Fig. S1, supporting information. Clearly, the bare ITO lm was homogeneous and at without continuous island-like clusters or aggregates (see Fig. S1a), while the surface morphology (see Fig. S1b) of [CuL](NO3)2 on ITO showed closely packed and randomly stacked clusters with diameters ranging from several hundreds nanometers to several micrometers, making the lm rough and jaggy in surface. The elemental compositions of both the bare ITO and the Cu(II) complex-coated ITO were also determined using the SEM coupled with the energy-dispersive X-ray (EDX) analyzer system, and the composition analysis results as shown in Table S1 in the supporting information, indicating that the composition elements of N and Cu were found in the spectrum of [CuL](NO3)2 lm on ITO, and were absent in that of the bare ITO. 3.2. UVvis absorption spectroscopy UVvis absorption spectra of [CuL](NO3)2 in acetonitrile and in the lm on ITO are compared in Fig. 2. The copper complex in acetonitrile showed an absorption peak centered at 600 nm which is assignable to the dd transition for a distorted tetragonal copper(II) complex (Karabocek and Karabocek, 1997; Williams et al., 2002). The copper complex lm on ITO exhibited a broad dd absorption band centered at $700 nm, which is red-shifted by 85 nm with respect to the acetonitrile solution, due most probably to aggregate formation of the copper complex in the lm due to the intermolecular pp* interactions. Note that the absorption for the copper complex lm extends into nearinfrared region which is desirable for solar light harvesting, and for photoelectric conversion accordingly.

Fig. 2. UVVis absorption spectra of [CuL](NO3)2 in acetonitrile (solid line) and the lm on ITO glass substrate (dashed line).

3.3. Cyclic voltammetry Cyclic voltammograms (see Fig. 3) of [CuL](NO3)2 on ITO showed a quasi-reversible redox couple with a halfwave potential E1/2 {E1/2 = (Epa + Epc)/2} being found at +0.088 V vs. SCE, which corresponds to the metal-based CuII/CuIII redox reaction (Ma et al., 2004; Fernandez-G et al., 2002; Yildirim et al., 2002; Raman et al., 2004; Pal et al., 2005; Farias and Bastos, 2009). A linear increase in cathodic peak currents with scan rates was obtained up to a scan rate of 0.4 V/s, indicating that the redox reaction was a surface-conned rather than a diusion controlled process (Bryce et al., 2003; Cheng and Dong, 2000; Cheng et al., 2001). From an onset oxidation potential Eonset(Ox) at +0.064 V vs. SCE (+0.305 V vs. normal hydrogen electrode, NHE), the value of the highest occupied molecular orbital (HOMO) energy level of the copper complex, EHOMO, was calculated according to Eq. (1) to be 4.80 eV with respect to the vacuum level based on a value of 4.74 eV for SCE with respect to the zero vacuum level (Wang et al., 2002).

Fig. 3. Cyclic voltammograms of a [CuL](NO3)2/ITO lm in 0.1 M aqueous Na2SO4 at dierent scan rates. Insert shows a plot of the peak currents vs. scan rates.

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EHOMO ef4:74 Eonset Oxg

The value of the lowest unoccupied molecular orbital (LUMO) energy level of the copper complex, ELUMO, was calculated according to Eq. (2) to be 3.23 eV by taking an onset absorption wavelength konset at 786 nm (see Fig. 2) for the Cu(II) complex on ITO DE ELUMO EHOMO 1240=konset 3.4. Photoelectrochemistry The eects of spin-coating solution concentrations on photoeletrochemical responses were studied. The photocurrents were found to enhance steadily with increasing concentrations of [CuL](NO3)2 from 1 to 4 mM, and remain almost constant over concentration range [Cu] = 430 mM (see Fig. S2). A concentration of 4 mM for the spin-coating acetonitrile solution was thus chosen for the preparation of the lms for the following photoelectrochemical measurements. Shown in Fig. 4 are the photocurrent responses for [CuL](NO3)2/ITO lm in aerated and Ar-degassed 1 M Na2SO4 aqueous solution at applied potentials of 0.4, 0.3 and 0.1 V vs. SCE under a white light irradiation (730 nm > k > 325 nm) of 70 mW/cm2. The prompt cathodic photocurrent responses were observed by switching the irradiation on, and the photocurrent traces were reproducible under several on/o cycles. At the applied potential of 0.4 V vs. SCE, the lm electrode in the aerated NaCl solution exhibited a stable cathodic photocurrent density of 71 lA/cm2; and as expected for the cathodic photocurrent generation, the cathodic photocurrent density of the lm electrode in the degassed solution was reduced to about 20 lA/cm2. In contrast, a bare ITO electrode showed a negligible response, demonstrating clearly that the copper complex was responsible for the photocurrent generation. It is noteworthy that the photocurrent density of 71 lA/ cm2 above-mentioned for [CuL](NO3)2 lm is the highest 2

among those listed in Table 1 for some representative thin lms previously reported (Ingrosso et al., 2009; Lang et al., 1998; Taniguchi et al., 1999; Yamada et al., 2003; Torres et al., 2000; Zou et al., 2010; Aoki et al., 1999; Wu et al., 1999; Han et al., 2007; Ju et al., 2010; Masayuki et al., 2002), and even more than 80-fold greater than those we previously reported for the electrostatically self-assembled lms of [Ru2(bpy)4(bpbp)2]4+/WO3 and [Ru2(bpy)4(eip)2]4+/PB under similar experimental conditions (Zou et al., 2010; Ju et al., 2010). An incident photon to current eciency (IPCE) value at a wavelength k of 660 nm for [CuL](NO3)2/ITO lm was calculated to be 1.1%, according to Eq. (3) (Nazeeruddin et al., 1993): IPCE% 1240I lA=cm2 knmP Inc: W=m2 3

Fig. 4. Photocurrent responses for [CuL](NO3)2/ITO lm in aerated (solid line) and N2-degassed (dotted line) 1 M Na2SO4 aqueous solution at applied potentials of 0.4, 0.3 and 0.1 V vs. SCE under a white light irradiation of 68 mW/cm2.

where I is the produced photocurrent, and PInc. is the incident light power at the wavelength k. Interestingly, the [CuL](NO3)2 lm is much thicker than the self-assembled and LangmuirBlodgett lms, and resulting in that strongly absorbed [CuL](NO3)2 lm at k = 660 nm exhibited IPCE value of only 1.1%, which still compares favorably with those for the lms listed in Table 1. It should be pointed out that this eciency value of 1.1% is much less than those reported for some Ru(II) complex-sensitized TiO2 nanocrystalline solar cells, e.g. the two solar cells we recently reported (Fan et al., 2009, 2010). The dependence of photocurrents on the applied bias voltages was also studied and the results are shown in Fig. 5. The photocurrents decreased with increasing bias voltages, demonstrating that the photocurrents were generated by electron moving from ITO electrode to the Cu(II) complex, and being cathodic. This cathodic photocurrent polarity was also evidenced by additions of electron acceptor methyl viologen (MV2+) and electron donor ascorbic acid into the electrolyte solution. It was found that photocurrents increased with increasing viologen concentrations over applied potential range from 0.2 V to 0 V, but almost disappeared in the presence of the ascorbic acid. The photocurrent action spectrum and UV/Visible absorption spectrum of [CuL](NO3)2/ITO lm are overlaid in Fig. 6. The both spectra are similar to each other, suggesting that the photocurrents originated from photoexcitation of [CuL](NO3)2 in the lm.To understand the photocurrent generation mechanism, one should look closely at the electron-transfer mechanism that took place within the lm. Fig. 7 shows the energy level arrangements for the species involved in the photocurrent generation processes, in which the reduction potentials of methyl viologen and O2 as well as Fermi level of ITO are taken to be 0.4, 0.26 and 0.3 V vs. NHE, respectively (Ju et al., 2010; Imahori et al., 2000). Clearly, the photocurrent was generated by following photoinduced electron transfer cascade: (1) photoexcitation of ground state copper complex resulted in excited complex [CuL]2+*, (2) and from which the electron was transferred to MV2+, and (3) thus oxidized copper

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Table 1 The comparisons of photocurrent density (J) under white light irradiation and the incident photon to current eciency (IPCE) of thin lms prepared by solvent evaporation (SE), self assembly, electrodeposition, and LangmuirBlodgett (LB) techniques. Filmsa [CuL](NO3)2 TIPCuPc/TiO2 NC odqi [Ru(bpy)2(bpy-Poly-tPA)]2+ H2P-C60 [Ru(bpy)2(dhbpy)]2+/PB [Ru2(bpy)4(bpbh)2]4+/WO3 Ru-Fc mtds [Ru(dcbpy)2(NCS)2]/dapv/ SWCNTs [Ru2(bpy)4(eip)2]4+/PB WO3/[Ru(bpy)3]2+/PSS
a

Film-forming technique SE SA LB LB SA LB SA LB LB SA SA Electrodeposition

J (lA/cm2) 71 0.015 0.350.46 0.16 4.5 0.8 1.7 0.0108 0.66 4.7

IPCE(%) 1.1 0.5 <0.01 0.23b 0.32 2.1 <0.01

Reference This work Ingrosso et al. (2009) Lang et al. (1998) Taniguchi et al. (1999) Yamada et al. (2003) Torres et al. (2000) Zou, et al. (2010) Aoki et al. (1999) Wu et al. (1999) Han et al. (2007) Ju et al. (2010) Masayuki et al. (2002)

Abbreviations: TIPCuPc = copper(II) tetrakis-(isopropoxy-carbonyl)-phthalocyanine; TiO2 NC = TiO2 nanocrystal; odqi = (E)-octadecyl-4-[2-(4dimethylaminophenyl)ethenyl]quinolinium iodide; bpy-Poly-tPA = 2,20 -bipyridine copolymerized with N-tert-pentylacrylamide; H2P-C60 = porphyrin fullerene dyad; bpy = 2,20 -bipyrizine; dhbpy = 4,40 -diheptadecyl-2,20 -bipyridine; PB = Prussian blue; bpbh = 1,6-bis-(2-(2-pyridyl)benzimidazoyl)hexane; RuFe = A copolymer containing Ru bipyridyl complex and ferrocene moieties; mtds = 1-methyl-2,4,6-tris[2-(30 -methoxy-40 -(octadecyloxy)phenyl)-ethenyl]pyridinium iodide; dcbpy = 2,20 -bipyridine-4,40 -dicarboxylic acid; dapv = di(3-aminopropyl)viologen; SWCNTs = single-walled carbon nanotubes; eip = 2,20 -[1,2-ethanediylbis(oxy-2,1-ethanediyloxy-4,1-phenylene)]bis- 1H-imidazo[4,5-f][1,10]phenanthroline; PSS = poly(sodium 4-styrensulfonate). b This IPCE value is obtained by multiplying the light harvesting eciency (LHE), LHE(k) = 110A(k), by reported APCE (the absorbed photon to current eciency) value.

Fig. 5. Dependence of photocurrents on the applied potentials. Fig. 7. The mechanism of cathodic photocurrent generation in ITO/ [CuL](NO3)2/MV2+ or O2 system.

of ITO, and between the LUMO level of [CuIIL]/[CuIIIL] and redox potential of electron donor O2 or MV2+. 4. Conclusions A copper(II) complex-modied ITO electrode was fabricated by the solvent-evaporation method. The modied electrode was demonstrated to exhibit good photoelectrochemical properties with a photocurrent density and an incident photon to current eciency (IPCE) values of as high as 71 lA/cm2 and 1.1%, respectively. The impressive photoelectric properties exhibited by the copper complex compare favorably with some representative sensitizers previously reported under similar experimental conditions, and but signicant lower than Ru(II) complex-sensitized TiO2 nanocrystalline solar cells. In view of its simple synthesis, low-cost and good photoelectrochemical properties, [CuL](NO3)2 complex is an attractive candidate for further

Fig. 6. The comparison of photocurrent action spectrum of [CuL](NO3)2/ ITO lm obtained at an applied potential of 0.4 V vs. SCE with an absorption spectrum of [CuL](NO3)2/ITO lm.

complex [CuL]3+ accepted electron from the Fermi level of ITO. It is conceivable that the high eciency photoelectric conversion could result from matching between the HOMO energy level of [CuIIL]/[CuIIIL] and the Fermi level

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molecular modication, e.g. by enhancing its molar extinction coecients and grafting an anchoring group, for applications in photoelectric devices. Acknowledgements The authors thank the National Natural Science Foundation (20771016, 20971016, and 90922004), Beijing Natural Science Foundation (2072011), the Fundamental Research Funds for the Central Universities, and Analytical and Measurements Fund of Beijing Normal University for nancial supports. Appendix A. Supplementary data Scanning electron micrographs of bare ITO and [CuL](NO3)2/ITO lm at top view under 70,000 magnication, and the eects of concentrations of the spin-coating acetonitrile solutions of the copper complex on the photocurrents obtained at a bias voltage of 0.1 V vs. SCE for [CuL](NO3)2/ITO lms were available from supplementary data. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/ j.solener.2011.04.018. References
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