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Solar Energy Materials & Solar Cells 77 (2003) 229237

A Cu2O=TiO2 heterojunction thin lm cathode for photoelectrocatalysis


Withana Siripala, Anna Ivanovskaya, Thomas F. Jaramillo, Sung-Hyeon Baeck, Eric W. McFarland*
Department of Chemical Engineering, University of California, Santa Barbara, CA 93106-5080, USA Received 15 July 2002; accepted 1 August 2002

Abstract A thin lm heterojunction photocathode was developed consisting of 100 nm of n-type titanium dioxide TiO2 cathode surface deposited on p-type cuprous oxide Cu2 O: The cuprous oxide was deposited electrochemically on Ti foil. A photocurrent of 0:7 mA=cm2 (at 1 V bias) and an open circuit photovoltage of 460 mV were obtained under an illumination of 700 W=m2 : The photoresponse as a function of pH demonstrated that the TiO2 lm protected the Cu2 O underlayer against corrosion. These results suggest that using a simple and inexpensive heterostucture conguration, the corrosion limitations of Cu2 O alone may be overcome while maintaining a relatively high efciency for photoelectrolysis. r 2002 Elsevier Science B.V. All rights reserved.
Keywords: Photocatalyst; Hydrogen; Photoelectrode; Heterojunction photocathode

1. Introduction Direct conversion of solar energy to chemical energy using semiconductor photoelectrodes has been of interest for many decades [16]. In particular, photoelectrolysis of water to produce hydrogen H2 has attracted attention because of the signicance of H2 as a clean, renewable fuel that could reduce the need for fossil fuels. The possibility of producing H2 using UV light was rst demonstrated by Fujishima and Honda in 1972 using the semiconductor material titanium dioxide TiO2 as a photoanode producing O2 and a platinum counter electrode [7]. Since
*Corresponding author. Tel.: +1-805-893-4343; fax: +1-805-893-4731. E-mail address: mcfar@engineering.ucsb.edu (E.W. McFarland). 0927-0248/02/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 7 - 0 2 4 8 ( 0 2 ) 0 0 3 4 3 - 4

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then, a large number of semiconductor materials have been investigated for photoelectrocatalytic electrodes for H2 production. Although many semiconductor materials have shown photocatalytic activity, most of them suffer from limitations including photocorrosion, poor solar spectrum absorption and the need of external bias [8]. Indeed, TiO2 is one of the most studied oxide semiconductor materials in this regard because of its stability in aqueous electrolytes. However, the band gap of TiO2 3:2 eV limits the absorption of sunlight to the high-energy portion (UV) of the solar spectrum. It has been reported earlier that attempts have been made to improve the absorption of visible light of TiO2 by incorporation of substitutional atoms into the lattice [9]. Although the incorporation of transition metals improves the visible light absorption in TiO2 electrodes, they have not yet been shown to be suitable for efcient water splitting reactions. Wide bandgap semiconductor materials 2:523:5 eV are typically more stable compared to narrow band gap 0:822 eV materials; however, the solar spectrum is more efciently absorbed by the narrow band gap materials. Thermodynamically, the energy requirement for the water splitting reaction is 1:23 eV: However, considering the loss mechanisms such as series resistance and the electrocatalytic overpotential, the optically produced electron hole pairs need an energy difference of approximately 2 eV for efcient photoelectrolysis [10]. Cuprous oxide is a semiconductor having a direct band gap of 2 eV which has been studied previously for application in solar energy converting devices (cf. [11] and references therein). A major attraction of cuprous oxide is that it is inexpensive, non-toxic, and readily available. Cuprous oxide can be prepared using many techniques including electrodeposition. The major disadvantages of cuprous oxide are that it is unstable with respect to anodic photocorrosion and it has a relatively low electrical conductivity [11]. It has been reported previously that heterostructure electrodes consisting of narrow gap semiconductors as light absorbers and wide gap semiconductors as stabilizers can be prepared for applications in photoelectrolysis [8,12,13]. These studies involved single crystal Si, GaAs, GaP [8,12,13], CdS [8,12], CdSe, ZnTe [8], InP [12], and GaAlAs [13] as the absorbers and polycrystalline thin lms TiO2 [8,12,13], Al2 O3 ; SnO2 [8,13], SrTiO3 [8] and Nb2 O5 ; SiN4 [13] for corrosion inhibition. In previous studies, a limitation was found in that the light generated minority carriers in the narrow gap absorber were not efciently transferred into the wide gap material and lost to recombination. The previous work, however, motivated us to try to nd new combinations of materials to form heterojunctions with improved band matching at the interface to facilitate the carrier transfer. In this investigation we have coupled the advantages of the chemical stability of TiO2 and the photon absorbance spectrum of Cu2 O with their conveniently aligned interface band structure to form n-TiO2 /p-Cu2 O heterostructure electrode. Specic problems and questions that we have addressed in this investigation include, (a) Is there a simple, reliable, and potentially low-cost fabrication procedure for heterojunction formation? (b) What are the photoelectrochemical properties of the

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junction? (c) Will the device perform stably over a range of pH values? (d) What can be done to optimize the performance?

2. Experimental Prior to lm deposition, titanium substrates were cleaned with detergent, dilute nitric acid and nally deionized water. Electrodeposition of Cu2 O lms on titanium substrates was accomplished in a three-electrode electrochemical cell containing aqueous solutions of 0:05 M sodium acetate and 0:05 M cupric acetate [14]. The temperature of the electrolyte was maintained at 601C and the electrolyte was continuously mixed using a magnetic stirrer. The counter electrode was a platinum wire and a Ag/AgCl electrode was used as the reference electrode. Electrodeposition was carried out under potentiostatic control at 200 mV vs Ag/AgCl electrode. Solutions were prepared with deionized water and reagent grade chemicals. Electrodeposition was carried out for 45 min and the resulting lms were calcined in air at 1501C for 30 min: The heterojunction was formed by electron beam evaporation of TiO2 100 nm over the electrodeposited Cu2 O from an anatase polycrystalline source (Super Conducting Materials, Inc.) under high vacuum PB106 Torr:: The Cu2 O=TiO2 electrodes were evaluated in an electrochemical cell containing a 0:1 M sodium acetate solution with a platinum counter electrode. The photoresponse was measured under illumination from a Xe lamp (700 W=m2 ; chopped at 0:1 Hz). In addition to the platinum counter electrode, a ruthenium dioxide RuO2 counter electrode was also tested for application with the Cu2 O=TiO2 electrode to reduce the anodic overpotential. In the preparation of RuO2 counter electrode the ruthenium metal was poteniostatically electrodeposited on Ti substrates for 5 min at 1 V vs Ag/AgCl using an aqueous solution of 50 mM ruthenium chloride. Then ruthenium metal electrode was anodized at 0:8 V vs Ag/AgCl in a 0:1 M H2 SO4 solution to obtain the RuO2 electrode. To investigate the dependence of the photoresponse and the stability of the electrode in the electrolyte, pH value of the sodium acetate solution in the PEC cell was varied with sodium hydroxide and sulfuric acid solutions. The spectral response of the electrode was measured using phase sensitive detection to monitor the photocurrent signal produced by a chopped monochromatic light source. The chopping frequency was 23 Hz: A monochromator (Oriel-Model 7240), potentiostat (EG&G 273A), lock-in amplier (Stanford Research-SR 530), and a chopper were used. The incident light intensity was measured using a radiometer (International Light IL 7200).

3. Results and discussion The photocurrent measured as a function of bias voltage under chopped illumination from the Cu2 O=TiO2 photocathode is shown in Fig. 1. A typical

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0.2 light off

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Fig. 1. Electrode current as a function of bias voltage for the Cu2 O=TiO2 heterojunction electrode in 0:1 M sodium acetate solution. The electrode is illuminated by a Xe lamp 700 W=m2 chopped at a frequency of 0:1 Hz: Typical p-type behavior is observed.

p-type photocurrent versus bias voltage behavior is observed. At 1 V bias, there is an output of 0:7 mW=cm2 : For standard Cu2 O electrodes of the same thickness the behavior is similar with an output of 0:6 mW=cm2 at 1 V bias at the same illumination (data not shown). Given the nearly identical photoconversions, the overall process of light absorption by the semiconductor, generation and separation of electron hole pairs, and transfer of electrons to the electrolyte and holes to the back contact, is occurring as efciently in the presence of the additional TiO2 layer as without it. Furthermore, although TiO2 is an n-type semiconductor and usually acts as a photoanode, the heterostructure behaves overall as a photocathode. A schematic diagram of the energy band structure of the Cu2 O=TiO2 heterojunction electrode in contact with the electrolyte is shown in Fig. 2. The TiO2 layer is very thin 100 nm and considered fully depleted while the band bending at the TiO2 / electrolyte interface is considered to be negligible. Light absorbed by the Cu2 O layer produces energetic electronhole pairs where the excited electrons are driven to the TiO2 /electrolyte interface via the conduction band of TiO2 while holes are driven to the counter electrode by way of the back contact. The net result is same as a Cu2 O electrode in contact with the electrolyte but the charge separation is now occurring at the Cu2 O=TiO2 interface instead. We have repeated the experiment for a Cu2 O=TiO2 electrode with a TiO2 layer of 150 nm thickness and similar behavior was observed. Fig. 3 shows the spectral responses of (a) Cu2 O=TiO2 ; (b) Cu2 O; and (c) TiO2 thin lm 100 nm electrodes. Compared to the Cu2 O electrode, the photoresponse of the Cu2 O=TiO2 electrode is enhanced at short wavelengths. In the Cu2 O electrode, the shorter wavelengths are absorbed closer to the Cu2 O=electrolyte interface and there is a high probability that the photogenerated electronhole pairs will recombine at the surface. On the other hand, in the Cu2 O=TiO2 electrode, the light absorption in

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Eabs (eV) ENHE (eV) -2 -3 -1 -4 0 -5 +1 -6 +2 -7 +3 -8 3.0 eV 2.0 eV H2O/H2 1.23 eV O2/H2O

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Cu2O

TiO2

Electrolyte

Fig. 2. Energy band diagram for the Cu2 O=TiO2 heterostructure. The TiO2 layer is very thin and considered fully depleted with negligible band bending at the electrolyte interface compared to the Cu2 O=TiO2 interface.

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Photocurrent (a.u.)

Cu2O/TiO2 Cu2O TiO2


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Fig. 3. Normalized spectral responses of (a) Cu2 O=TiO2 electrode (1 V bias), (b) Cu2 O (1 V bias) electrode and (c) TiO2 (0 V bias) thin lm electrode in 0:1 M sodium acetate solution. Solid lines are added to guide the eye.

this wavelength range is at the pn junction and there the recombination of photogenerated charge carriers is expected to be minimal. Therefore, we can expect an enhancement of photocurrent of the Cu2 O=TiO2 electrode in the short wavelength region. Also, Fig. 3 shows the enhancement and the extension of the spectral response to the visible wavelength region in the Cu2 O=TiO2 electrode as compared with the TiO2 electrode.

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Catalytically the system is limited by the Pt counter electrode. The holes generated by photon absorption are collected at the photocathode Ti back contact and are balanced through the external circuit by oxidation of water at the counter electrode. The Pt counter electrode has a relatively high over potential for oxygen evolution (see [15] and references cited therein). Ruthenium dioxide is known to be an excellent electrolcatalyst for O2 production with a lower overpotential [15]. Fig. 4 shows the photoresponses of the Cu2 O=TiO2 electrode (a) with a Pt counter electrode and
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Fig. 4. The Cu2 O=TiO2 heterojunction electrode photocurrent in 0:1 M sodium acetate solution, under a chopped light illumination 40 W=m2 ; with (a) RuO2 counter electrode, (b) Pt counter electrode. Area of each counter electrode is 2 cm2 : A signicant increase in the photocurrent is observed due to the lower oxidation overpotential of the RuO2 counter electrode. Solid line is added to guide the eye.

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(b) with a RuO2 counter electrode, separately. The area of each counter electrode is 2 cm2 : The use of a RuO2 counter electrode results in a signicant increase in the photocurrent. Thus, the added advantage of the catalytic activity for O2 production at the RuO2 counter electrode can be utilized in the Cu2 O=TiO2 as compared with the conventional TiO2 photoanode where O2 is produced at the TiO2 electrode. The dependence of the electrolyte pH on the photoresponse is shown in Fig. 5. The magnitude of the photocurrent of the Cu2 O=TiO2 electrode strongly depends on the pH of the electrolyte indicating a very strong correlation between the charge transfer kinetics and the pH of the electrolyte. The behavior was entirely reversible and not due to electrode corrosion. It is important to note that photogenerated electrons are producing a cathodic reaction at the TiO2 =electrolyte interface. In general, as the TiO2 is an n-type semiconductor, TiO2 electrodes produce photoanodic reactions. Since the rate of the band edge shifting of TiO2 with the pH of the electrolyte is same as the rate of change of the position of the redox level of H [16], strong dependence of the cathodic reaction rate with the pH is not expected [5]. We have observed that the Cu2 O=TiO2 photoelectrode can be operated in many electrolytes where the unprotected Cu2 O electrode is unstable and not operative [17]. This electrode may also be used for electrolysis of species other than water provided that the redox potentials are at the correct positions with respect to the band positioning of Cu2 O and TiO2 : It is important to note that the full band gap energy of Cu2 O is not available for electrolysis. This is because the loss of energy of the electrons when they are transferred to the conduction band of TiO2 and of the holes when they are transferred to the back contact. Therefore, a part of the energy required for the reactions may have to be provided by an applied external bias for certain reactions depending on the redox potentials. Particularly, an external bias is required for the photoelectrolysis of water with the Cu2 O=TiO2 electrode as is required by the Cu2 O electrode [17]. The electrode, however, is now more stable due to coverage by TiO2

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Photocurrent (mA/cm )

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0.10 4 6 8 10 12

pH
Fig. 5. Photocurrent of the Cu2 O=TiO2 heterojunction electrode (1 V bias) in 0:1 M sodium acetate solution at different electrolyte pH values. Illumination intensity 350 W=m2 :

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layer. The absolute efciency for H2 generation of the heterostructure and RuO2 counter electrode was measured using a UV ltered tungsten lamp at an illumination intensity of 1500 W=m2 and found that the photocurrent was 390 mA=cm2 which is equivalent to 1:6 106 mM H2 =W: Assuming an energy equivalent of 2:8 105 J=mol for H2 the energy conversion efciency (including the required bias, 1 V at 390 mA) was 0.05%.

4. Conclusions We have developed a heterojunction photocathode consisting of electro-deposited p-type Cu2 O and n-type TiO2 deposited by physical vapor deposition. The observed photoresponse of the electrode in electrolyte demonstrated efcient light induced charge carrier generation at the pn junction of the Cu2 O=TiO2 electrode. Although the electrode requires an external bias to drive the photoelectrolysis of water (similar to the Cu2 O electrode alone), the TiO2 lm successfully protects the Cu2 O lm against photocorrosion without diminishing performance. We have also demonstrated the possibility of utilizing a RuO2 counter electrode to enhance the efciency of the photoelectrode. This investigation demonstrates that visible light induced photocathodic reactions are possible with a Cu2 O=TiO2 heterojunction electrode with specic advantages over TiO2 photoanodes which require UV light and Cu2 O photocathodes which suffer from rapid corrosion.

Acknowledgements The research was supported by the Hydrogen Program of the Department of Energy (DOE, Grant No. DER-FC36-01G011092) and the NSF-MRSEC funded Materials Research Laboratory (UCSB).

References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] A.J. Nozik, Ann. Rev. Phys. Chem. 29 (1978) 189. A.J. Bard, J. Photochem. 10 (1979) 59. H. Gerischer, Top. Appl. Phys. 31 (1979) 115. M.S. Wrighton, Acc. Chem. Res. 12 (1979) 303. M. Tomkiewicz, H. Fay, J. Appl. Phys. 18 (1979) 1. R. Memming, Electrochim. Acta 25 (1980) 77. A. Fujishima, K. Honda, Nature 238 (1972) 37. H.P. Maruska, A.K. Ghosh, Sol. Energy Mater. 1 (1979) 411. H.P. Maruska, A.K. Ghosh, Sol. Energy Mater. 1 (1979) 237. H.P. Maruska, A.K. Ghosh, Sol. Energy Mater. 20 (1978) 443. B.P. Rai, Sol. Cells 25 (1988) 265. P.A. Kohl, S.N. Frank, A.J. Bard, J. Electrochem. Soc. 124 (1977) 225. M. Tomkiewicz, J.M. Woodal, J. Electrochem. Soc. 124 (1977) 1436.

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[14] W. Siripala, L.D.R.D. Perera, K.T.L. De Silva, J.K.D.S. Jayanetti, I.M. Dharmadasa, Sol. Energy Mater. Sol. Cells 44 (1996) 251. [15] S. Trasatti, G. Lodi, in: S. Trasatti (Ed.), Electrodes of Conductive Metallic Oxides, Part B, Elsevier, Amsterdam, 1981, p. 521. [16] H. Gerischer, J. Vac. Sci. Tech. 15 (4) (1978) 1422. [17] A.J. Nozik, R. Memming, J. Phys. Chem. 100 (1996) 13061.

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