Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
1 Institute
of Chemical Sciences and Engineering, Ecole Polytechnique Fdrale de Lausanne, Laboratory of Photonics and Interfaces, Station 6, CH-1015
Lausanne, Switzerland, 2 Interdisciplinary Centre for Electron Microscopy, Ecole Polytechnique Fdrale de Lausanne, Station 12, CH-1015 Lausanne,
Switzerland. Present address: Argonne National Lab, Material Science Division, Argonne, Illinois 60439, USA. *e-mail: ethimsen@anl.gov.
456
ARTICLES
a
CB
CB
+0.00
2H+ + 2e <> H2
+0.47
+0.60
2
0
4
J (mA cm2)
O2 +
4e
J (mA cm2)
+1.23
4H+ +
CB
5
6
VB
Cu2O
VB
ZnO
2
4
6
8
10
15
20
Time (min)
TiO2
0.25
0.30
0.35
0.40
0.45
E (V) versus RHE
0.50
0.55
b
0
(1)
2
3
2
J (mA cm2)
Cu2 O + 2e + 2H+ Cu + H2 O
J (mA cm2)
2
4
6
7
8
0.1
10
Time (min)
0.2
0.3
E (V) versus RHE
0.4
15
20
0.5
457
ARTICLES
a
TiO2
ZnO:Al
Pt
Cu2O
FTO
Au
500 nm
barriers in the protective layer resulting from the high Al2 O3 content
of the structure (expected 6.6 at.% for Al in sample 5).
It is known that Al3+ doping in ZnO can increase the electron
concentration30,31 , but we do not believe this is the origin of
the phenomenon observed here. The carrier concentration in the
ZnO layer did increase with Al2 O3 incorporation (Supplementary
Fig. S3c), but the initial photocurrents of sample 3 and sample
4 were approximately the same. Furthermore, by comparing
the measured carrier concentration to the expected Al3+ atom
concentration (Supplementary Information), we estimate that 90%
of the Al3+ atoms were not donating electrons to the conduction
band, and must therefore be serving a different role.
When the electrodes with the protective layers were subjected to
a mild heat treatment at 200 C in air for 45 min before platinum
deposition, the stability was further improved and accompanied
by a drop in the initial photocurrent (samples 8 and 9). The
effect of aluminium addition to the ZnO remained after annealing,
and the electrode with 0.17 nm Al2 O3 layers spaced every 4 nm
exhibited an increased stability of 78% after 20 min (sample 9),
compared with 50% for the ZnO-alone case (sample 8). The
observed decrease in initial photocurrent can be explained by the
increased resistivity for both ZnO and Al:ZnO (Supplementary
Fig. S3b) compared with the corresponding as-deposited films,
especially for the undoped ZnO/TiO2 film, which was too resistive
for the Hall coefficient to be measured by our instrument. The
increased stability could have resulted from removal of residual
water from the ALD layers at 200 C, or could have derived from
restructuring of the layers at the interface. It is worth noting that to
the knowledge of the authors, the initial photocurrents of sample 9
and the as-deposited electrode with the same configuration
(sample 4) exhibited higher photocurrents, 5.7 mA cm2 and
7.6 mA cm2 respectively, than any oxide-based photoelectrode
previously published under AM 1.5 illumination. The incident
photon-to-current efficiency for an annealed electrode held at
0 V versus RHE is presented in Supplementary Fig. S6 with the
corresponding J V plot. The electrode showed a photoresponse
from 350 to 600 nm, and the incident photon-to-current efficiency
was 40% between 350 and 480 nm.
The production of H2 gas was confirmed by the formation
of bubbles evolving off the photocathode immediately after
illumination and during the stability measurement (Supplementary
Fig. S5). After passing 0.58 C through the photocathode under
continuous illumination at 0 V versus RHE, an amount of
75 10 l of H2 gas was detected by volume displacement
measurements, which was consistent with the expected amount of
67 l, corresponding to a Faradaic efficiency of close to 100%.
The evidence is consistent with chemical stabilization of
Cu2 O and indicates that the photocurrent decay was not due
to the degradation of the photoactive material. We carried out
Table 1 | Summary of PEC performance for the different ALD layers investigated.
Sample ID
Cu2 O
thickness
(m)
ALD
post-treatment
J at 0 V
versus RHE
(mA cm2 )
J/J0 after
20 min at 0 V
versus RHE (%)
1
2
3
4
5
6
7
8
9
Bare
11 nm TiO2
21 nm ZnO/11 nm TiO2
5 (4 nm ZnO/0.17 nm Al2 O3 )/11 nm TiO2
10 (2 nm ZnO/0.17 nm Al2 O3 )/11 nm TiO2
21 nm ZnO/0.9 nm Al2 O3 /11 nm TiO2
0.9 nm Al2 O3 /21 nm ZnO/11 nm TiO2
21 nm ZnO/11 nm TiO2
5 (4 nm ZnO/0.17 nm Al2 O3 )/11 nm TiO2
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
As-deposited
As-deposited
As-deposited
As-deposited
As-deposited
As-deposited
As-deposited
200 C, 45 min, air
200 C, 45 min, air
0
0
14
33
53
52
17
50
78
458
Dark scan 2
Dark scan 3
Light scan 2
Light scan 3
Dark scan 2
Dark scan 3
Light scan 2
Light scan 3
J (mA cm2)
J (mA cm2)
ARTICLES
1
0
0.2
0.4
0.6
0.8
E (V) versus RHE
1.0
1.2
0.2
0.4
0.6
0.8
1.0
1.2
Figure 4 | Cyclic voltammetry of the bare and surface-protected Cu2 O electrode. a,b, Cyclic voltammetry on an as-deposited bare Cu2 O electrode (a)
and on a Cu2 O/5 (4 nm ZnO/0.17 nm Al2 O3 )/11 nm TiO2 /Pt electrode after PEC characterization (b). The absence of any features other than
photoreduction of water in the cyclic voltammogram of the protected electrode shows its chemical stability.
459
ARTICLES
Zn 2p
1,050
1,040
1,035
1,030
Intensity (cps)
1,045
250
500
750
1,000
1,250
1,500
1,750
2,000
2,250
2,500
2,750
1,025
1,020
0
30
60
Pt 4f
82
78
76
Intensity (cps)
80
100
200
300
400
500
600
700
74
72
70
68
66
0
30
60
Ti 2p
460
455
Intensity (cps)
465
250
500
750
1,000
1,250
1,500
1,750
2,000
2,250
2,500
2,750
3,000
3,250
3,500
3,750
450
0
30
60
Figure 5 | Contour plots for the XPS signals of Zn, Pt and Ti from the
barrier layer. XPS spectra with depth profile analysis on a Cu2 O/5
(4 nm ZnO/0.17 nm Al2 O3 )/11 nm TiO2 /Pt electrode after
photoelectrochemical characterization. The XPS spectra acquisition was
carried out after 15 s cycles of Ar+ sputtering. The data were interpolated
between each XPS spectra, but were not smoothed.
Methods
Cu2 O electrodeposition. The Cu2 O thin films were deposited by electrodeposition
from a basic solution of lactate-stabilized copper sulphate. The deposition substrate
(working electrode) was TEC-15 fluorine-doped tin oxide (FTO, NGS glass)
coated with 200 nm of Au, deposited by thermal evaporation. An adhesion layer
of 20 nm of Cr was deposited by thermal evaporation on the FTO substrate before
gold deposition. Au-coated substrates were chosen over indium tin oxide or FTO
because the deposition reproducibility was better. The plating bath was 0.2 M
CuSO4 (Sigma Aldrich) and 3 M lactic acid (Fisher Scientific) solution in deionized
water with 0.5 M K2 HPO4 (Sigma) buffer. The bath pH was adjusted to pH 12
by adding a controlled amount of 2 M KOH. The temperature of the bath was
maintained at 30 C using a heating plate with an in situ temperature probe. The
Cu2 O thin films were deposited at a constant current density of 0.1 mA cm2
(Galvanostatic mode) for 220 min using a source meter (2400, Keithley) in a
two-electrode configuration (a Pt mesh served as the counter electrode), which
resulted in a film thickness of 1.3 m, as measured by a profilometer (Alpha-step,
Trencor). The parameters for Cu2 O electrodeposition from Cu (ii) lactate solution
were optimized for photoelectrochemical response and the details will be given
in a separate article.
Atomic layer deposition. Ultrathin protective layers of n-type oxides were
deposited on the surface of the Cu2 O thin films using a thermal ALD system
(Savannah 100, Cambridge Nanotech). Before ALD, to remove any residual
organic contaminants remaining from the electrodeposition38 and to saturate the
surface with hydroxyl groups in preparation for ALD, the Cu2 O samples were
dipped in 30% H2 O2 in water and immediately rinsed with copious amounts of
deionized water. The H2 O2 rinsing procedure was repeated twice. The ALD was
carried out at a substrate temperature of 120 C. This temperature was chosen
because a slight discolouration (and decrease in activity) of the Cu2 O thin film
was observed if deposition was carried out at higher temperatures of 200 C. Zinc
oxide (ZnO) was deposited using diethyl zinc (Tprecursor = room temperature) and
H2 O (Tprecursor = room temperature) as the Zn and O precursors, respectively.
Each precursor was held in the chamber for 2.0 s, followed by a 15.0 s nitrogen
purge. The GPC was measured by ellipsometry on films deposited on optically
polished silicon wafers with a native surface oxide, and for ZnO was 2.0 .
Aluminium-doped ZnO (Al:ZnO) was deposited by running 1 cycle of trimethyl
aluminium (Tprecursor = room temperature) and water after the specified number of
diethyl zinc and water cycles, either 20 or 10. For reference, Al2 O3 grown at these
conditions exhibited a GPC of 1.7 . Titanium dioxide (TiO2 ) was deposited using
titanium tetraisopropoxide (Tprecursor = 80 C) and H2 O as the Ti and O precursors,
respectively. Each precursor was held in the chamber for 2.0 s followed by a 15.0 s
nitrogen purge. The GPC for TiO2 was 0.28 . The cycle numbers were varied to
control the film thickness, which was calculated using the GPC values. Following
ALD, the samples were platinized either as-deposited or after heat treatment at
200 C for 45 min in air.
Cocatalyst deposition. To enhance the kinetics of the water reduction reaction,
platinum nanoparticles were potentiostatically electrodeposited in the dark from a
solution of 1 mM H2 PtCl6 in deionized water at 0.1 V versus Ag/AgCl for 15 min.
Epoxy resin was applied before platinization to cover any exposed FTO or Au.
Structural characterization. The electrodes were characterized by SEM, XRD
and XPS. The morphology of the films was characterized using a high-resolution
scanning electron microscope (FEI XL30 SFEG). XRD patterns were acquired with
a Bruker D8 Discover diffractometer in the BraggBrentano mode, using Cu K
radiation (1.540598 ) and a Ni -filter. Spectra were acquired with a linear
NATURE MATERIALS | VOL 10 | JUNE 2011 | www.nature.com/naturematerials
References
1. Khaselev, O. & Turner, J. A. A monolithic photovoltaicphotoelectrochemical device for hydrogen production via water splitting.
Science 280, 425427 (1998).
2. Aharon-Shalom, E. & Heller, A. Efficient p-InP(Rh-H alloy) and p-InP(ReH
alloy) hydrogen evolving photocathodes. J. Electrochem. Soc. 129,
28652866 (1982).
3. Marsen, B., Cole, B. & Miller, E. L. Photoelectrolysis of water using thin
copper gallium diselenide electrodes. Sol. Energy Mater. Sol. Cells 92,
10541058 (2008).
4. Fernandez, A. M. et al. Photoelectrochemical characterization of the
Cu(In,Ga)S2 thin film prepared by evaporation. Sol. Energy Mater. Sol. Cells
85, 251259 (2005).
5. Hara, M. et al. Cu2 O as a photocatalyst for overall water splitting under visible
light irradiation. Chem. Commun. 357358 (1998).
6. de Jongh, P. E., Vanmaekelbergh, D. & Kelly, J. J. Photoelectrochemistry of
electrodeposited Cu2 O. J. Electrochem. Soc. 147, 486489 (2000).
7. Siripala, W., Ivanovskaya, A., Jaramillo, T. F., Baeck, S. H. & McFarland, E. W.
A Cu2 O/TiO2 heterojunction thin film cathode for photoelectrocatalysis.
Sol. Energy Mater. Sol. Cells 77, 229237 (2003).
8. Hu, C. C., Nian, J. N. & Teng, H. Electrodeposited p-type Cu2 O as photocatalyst
for H-2 evolution from water reduction in the presence of WO3. Sol. Energy
Mater. Sol. Cells 92, 10711076 (2008).
9. Nian, J. N., Hu, C. C. & Teng, H. Electrodeposited p-type Cu2 O for H-2
evolution from photoelectrolysis of water under visible light illumination.
Int. J. Hydrog. Energy 33, 28972903 (2008).
10. Barreca, D. et al. The potential of supported Cu2 O and CuO nanosystems in
photocatalytic H-2 production. ChemSusChem 2, 230233 (2009).
11. Morales, J. et al. Electrodeposition of Cu2 O: An excellent method for obtaining
films of controlled morphology and good performance in Li-ion batteries.
Electrochem. Solid State Lett. 8, A159A162 (2005).
12. Lee, Y. H. et al. Fabrication and characterization of Cu2 O nanorod
arrays and their electrochemical performance in Li-ion batteries.
Electrochem. Solid State Lett. 9, A207A210 (2006).
13. Bijani, S. et al. Nanostructured Cu2 O thin film electrodes prepared by
electrodeposition for rechargeable lithium batteries. Thin Solid Films 515,
55055511 (2007).
14. Katayama, J., Ito, K., Matsuoka, M. & Tamaki, J. Performance of Cu2 O/ZnO
solar cell prepared by two-step electrodeposition. J. Appl. Electrochem. 34,
687692 (2004).
15. Akimoto, K. et al. Thin film deposition of Cu2 O and application for solar cells.
Sol. Energy 80, 715722 (2006).
ARTICLES
16. Jeong, S. S., Mittiga, A., Salza, E., Masci, A. & Passerini, S.
Electrodeposited ZnO/Cu2 O heterojunction solar cells. Electrochim. Acta 53,
22262231 (2008).
17. Cui, J. B. & Gibson, U. J. A simple two-step electrodeposition of Cu2 O/ZnO
nanopillar solar cells. J. Phys. Chem. C 114, 64086412 (2010).
18. Graetzel, M. Photoelectrochemical cells. Nature 414, 338344 (2001).
19. de Jongh, P. E., Vanmaekelbergh, D. & Kelly, J. J. Cu2 O: Electrodeposition and
characterization. Chem. Mater. 11, 35123517 (1999).
20. Sculfort, J. L., Guyomard, D. & Herlem, M. Photoelectrochemical
characterization of the p-Cu2 O-non aqueous electrolyte junction. Electrochim.
Acta 29, 459465 (1984).
21. Engel, C. J., Polson, T. A., Spado, J. R., Bell, J. M. & Fillinger, A.
Photoelectrochemistry of porous p-Cu2 O films. J. Electrochem. Soc. 155,
F37F42 (2008).
22. George, S. M. Atomic layer deposition: An overview. Chem. Rev. 110,
111131 (2010).
23. Hwang, Y. J., Boukai, A. & Yang, P. High density n-Si/n-TiO2 core/shell
nanowire arrays with enhanced photoactivity. Nano Lett. 9, 410415 (2009).
24. Shan, C. X., Hou, X. H. & Choy, K. L. Corrosion resistance of TiO2 films
grown on stainless steel by atomic layer deposition. Surf. Coat. Technol. 202,
23992402 (2008).
25. Guidi, F. et al. Electrochemical anticorrosion performance evaluation of
Al2 O3 coatings deposited by MOCVD on an industrial brass substrate.
Electrochim. Acta 50, 46094614 (2005).
26. Du, X. H., Zhang, K., Holland, K., Tombler, T. & Moskovits, M. Chemical
corrosion protection of optical components using atomic layer deposition.
Appl. Opt. 48, 64706474 (2009).
27. Galliano, P., De Damborenea, J. J., Pascual, M. J. & Duran, A. Solgel
coatings on 316L steel for clinical applications. J. SolGel Sci. Technol. 13,
723727 (1998).
28. Heller, A. Hydrogen-evolving solar cells. Science 223, 11411148 (1984).
29. Standridge, S. D., Schatz, G. C. & Hupp, J. T. Toward plasmonic solar cells:
Protection of silver nanoparticles via atomic layer deposition of TiO2 . Langmuir
25, 25962600 (2009).
30. Elam, J. W., Routkevitch, D. & George, S. M. Properties of ZnO/Al2 O3 alloy
films grown using atomic layer deposition techniques. J. Electrochem. Soc. 150,
G339G347 (2003).
31. Agashe, C. et al. Efforts to improve carrier mobility in radio frequency sputtered
aluminium doped zinc oxide films. J. Appl. Phys. 95, 19111917 (2004).
32. Lee, D-J. et al. Structural and electrical properties of atomic layer deposited
Aldoped ZnO films. Adv. Funct. Mater. 21, 448455 (2011).
33. Yasomanee, J. P. & Bandara, J. Multi-electron storage of photoenergy
using Cu2 OTiO2 thin film photocatalyst. Sol. Energy Mater. Sol. Cells 92,
348352 (2008).
34. Xiong, L. B. et al. Visible-light energy storage by Ti3+ in TiO2 /Cu2 O bilayer
film. Chem. Lett. 38, 11541155 (2009).
35. ORegan, B., Grtzel, M. & Fitzmaurice, D. Optical electrochemistry I:
Steady-state spectroscopy of conduction-band electrons in a metal oxide
semiconductor electrode. Chem. Phys. Lett. 183, 8993 (1991).
36. Howe, R. F. & Gratzel, M. EPR observation of trapped electrons in colloidal
titanium dioxide. J. Phys. Chem. 89, 44954499 (1985).
37. Kaise, M. et al. Electron spin resonance studies of photocatalytic interface
reactions of suspended M/TiO2 (M = Pt, Pd, Ir, Rh, Os, or Ru) with alcohol
and acetic acid in aqueous media. Langmuir 10, 13451347 (1994).
38. Nadesalingam, M. P. et al. Effect of vacuum annealing on the surface chemistry
of electrodeposited copper(i) oxide layers as probed by positron annihilation
induced auger electron spectroscopy. Langmuir 23, 18301834 (2007).
Acknowledgements
The research leading to these results has received funding from the European
Communitys Seventh Framework Programme (FP7/2007-2013) under grant agreement
no. 227179 (NanoPEC). We would also like to thank the Swiss Federal Office of Energy
(Project number 102326, PECHouse) and the Energy Center at EPFL for financial
support. We acknowledge N. Xanthopoulos from the Interdisciplinary Centre for
Electron Microscopy (CIME) at EPFL for helping in the XPS characterization. E.T. would
also like to thank A. Martinson at Argonne National Laboratory for helpful discussions
about aluminium-doped zinc oxide synthesized by ALD.
Author contributions
A.P. and E.T. designed the experiments. A.P. carried out electrodeposition, PEC
measurements, SEM and XRD. ALD was carried out by E.T. Faradaic efficiency
measurements were carried out by K.S. XPS was carried out by V.L. M.G. supervised the
project. All of the authors discussed and analysed the data.
Additional information
The authors declare no competing financial interests. Supplementary information
accompanies this paper on www.nature.com/naturematerials. Reprints and permissions
information is available online at http://www.nature.com/reprints. Correspondence and
requests for materials should be addressed to E.T.
461