CRITERIOS DE ACCESIBILIDAD A LAS PÁGINAS WEB DE LAS ADMINISTRACIONES

I would like to acknowledge Xinxin Li and Yukun Liu for their help preparing electrodes and performing control experiments, Haiyan Tan for performing STEM and analysis, Rongyue Wang for providing cross-sectional SEM images, Jeffery T. Koberstein for insightful conversations and guidance on fabricating the SiOx films, and Thomas P. Moffat and Chathuranga De Silva for assistance with XPS measurements and analysis. Dr. Esposito and I acknowledge Columbia University (start-up funds) and the National Science Foundation (NSF) Center for Precision Assembly of Superstratic and Superatomic Solids for funding (DMR-1420634).

3.8 References

(1) Lewis, N. S.; Nocera, D. G. Powering the Planet: Chemical Challenges in Solar Energy Utilization. Proc. Natl. Acad. Sci. 2006, 103 (43), 15729–15735.

(2) Safaei, H.; Keith, D. W. How Much Bulk Energy Storage Is Needed to Decarbonize Electricity? Energy Environ. Sci. 2015.

(3) Newman, J.; Hoertz, P. G.; Bonino, C. a.; Trainham, J. A. Review: An Economic -4 -2 0 2 4 -0.4 0.0 0.4 0.8 1.2 Cur ren t de ns ity / m A c m -2 Potential / V vs. Ag|AgCl 2 nm SiO_x/SiO₂/pSi Simulated fit -4 -2 0 2 4 0.0 0.2 0.4 0.6 Cur ren t de ns ity / m A c m -2 Potential / V vs. Ag|AgCl 1.5 nm SiO₂/pSi Simulated fit

b)

a)

116

Perspective on Liquid Solar Fuels. J. Electrochem. Soc. 2012, 159 (10), A1722–A1729. (4) Chen, X.; Shen, S.; Guo, L.; Mao, S. S. Semiconductor-Based Photocatalytic Hydrogen

Generation. Chem. Rev. 2010, 110 (11), 6503–6570.

(5) Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; Mi, Q.; Santori, E. A.; Lewis, N. S. Solar Water Splitting Cells. Chem. Rev. 2010, 110 (11), 6446–6473.

(6) Gratzel, M. Photoelectrochemical Cells. Nature 2001, 414, 338–344.

(7) Turner, J.; Sverdrup, G.; Mann, M. K.; Maness, P.-C.; Kroposki, B.; Ghirardi, M.; Evans, R. J.; Blake, D. Renewable Hydrogen Production. Int. J. Energy Res. 2007, 32, 379–407. (8) McKone, J. R.; Lewis, N. S.; Gray, H. B. Will Solar-Driven Water-Splitting Devices See

the Light of Day? Chem. Mater. 2014, 26, 407–414.

(9) Lewis, N. S. An Integrated, Systems Approach to the Development of Solar Fuel Generators. Electrochem. Soc. 2013, 43–49.

(10) Pinaud, B. A.; Benck, J. D.; Seitz, L. C.; Forman, A. J.; Chen, Z.; Deutsch, T. G.; James, B. D.; Baum, K. N.; Baum, G. N.; Ardo, S.; et al. Technical and Economic Feasibility of Centralized Facilities for Solar Hydrogen Production via Photocatalysis and Photoelectrochemistry. Energy Environ. Sci. 2013, 6 (7), 1983.

(11) Zhu, T.; Chong, M. N. Prospects of Metal–insulator–semiconductor (MIS) Nanojunction Structures for Enhanced Hydrogen Evolution in Photoelectrochemical Cells: A Review.

Nano Energy 2015, 12, 347–373.

(12) Muñoz, A. G.; Lewerenz, H. J. Advances in Photoelectrocatalysis with Nanotopographical Photoelectrodes. ChemPhysChem 2010, 11 (8), 1603–1615.

(13) Lewerenz, H. J.; Skorupska, K.; Muñoz, A. G.; Stempel, T.; Nüsse, N.; Lublow, M.; Vo- Dinh, T.; Kulesza, P. Micro- and Nanotopographies for Photoelectrochemical Energy Conversion. II: Photoelectrocatalysis – Classical and Advanced Systems. Electrochim. Acta 2011, 56, 10726–10736.

(14) Esposito, D. V; Levin, I.; Moffat, T. P.; Talin, A. A. H2 Evolution at Si-Based Metal- Insulator-Semiconductor Photoelectrodes Enhanced by Inversion Channel Charge Collection and H Spillover. Nat. Mater. 2013, 12 (6), 562–568.

(15) Kenney, M. J.; Gong, M.; Li, Y.; Wu, J. Z.; Feng, J.; Lanza, M.; Dai, H. High-Performance Silicon Photoanodes Passivated with Ultrathin Nickel Films for Water Oxidation. Science 2013, 342 (6160), 836–840.

(16) Choi, M. J.; Jung, J.-Y.; Park, M.-J.; Song, J.-W.; Lee, J.-H.; Bang, J. H. Long-Term Durable Silicon Photocathode Protected by a Thin Al2O3/SiOx Layer for Photoelectrochemical Hydrogen Evolution. J. Mater. Chem. A 2014, 2, 2928.

117

(17) Hill, J. C.; Landers, A. T.; Switzer, J. A. An Electrodeposited N-Si/SiOx/Co/CoOOH Inhomogeneous Metal-Insulator-Semiconductor Junction for Efficient Photoelectrochemical Water Oxidation. Nat. Mater. 2015, 14, 6751–6755.

(18) Chen, Y. W.; Prange, J. D.; Dühnen, S.; Park, Y.; Gunji, M.; Chidsey, C. E. D.; McIntyre, P. C. Atomic Layer-Deposited Tunnel Oxide Stabilizes Silicon Photoanodes for Water Oxidation. Nat. Mater. 2011, 10 (7), 539–544.

(19) Scheuermann, A. G.; Prange, J. D.; Gunji, M.; Chidsey, C. E. D.; McIntyre, P. C. Effects of Catalyst Material and Atomic Layer Deposited TiO2 Oxide Thickness on the Water Oxidation Performance of Metal-Insulator-Silicon Anodes. Energy Environ. Sci. 2013, 4 (8), 1166–1169.

(20) Hu, S.; Shaner, M. R.; Beardslee, J. A.; Lichterman, M.; Brunschwig, B. S.; Lewis, N. S. Amorphous TiO₂ Coatings Stabilize Si, GaAs, and GaP Photoanodes for Efficient Water Oxidation. Science 2014, 344 (6187), 1005–1009.

(21) Boettcher, S. W.; Warren, E. L.; Putnam, M. C.; Santori, E. A.; Turner-Evans, D.; Kelzenberg, M. D.; Walter, M. G.; McKone, J. R.; Brunschwig, B. S.; Atwater, H. A.; et al. Photoelectrochemical Hydrogen Evolution Using Si Microwire Arrays. J. Am. Chem. Soc. 2011, 133, 1216–1219.

(22) Seger, B.; Laursen, A. B.; Vesborg, P. C. K.; Pedersen, T.; Hansen, O.; Dahl, S.; Chorkendorff, I. Hydrogen Production Using a Molybdenum Sulfide Catalyst on a Titanium-Protected n(+)p-Silicon Photocathode. Angew. Chem. Int. Ed. Engl. 2012, 51 (36), 9128–9131.

(23) Seger, B.; Pedersen, T.; Laursen, A. B.; Vesborg, P. C. K. K.; Hansen, O.; Chorkendorff, I. Using TiO2 as a Conductive Protective Layer for Photocathodic H2 Evolution. J. Am.

Chem. Soc. 2013, 135 (3), 1057–1064.

(24) Laursen, A. B.; Pedersen, T.; Malacrida, P.; Seger, B.; Hansen, O.; Vesborg, P. C. K.; Chorkendorff, I. MoS2-an Integrated Protective and Active Layer on n(+)p-Si for Solar H2 Evolution. Phys. Chem. Chem. Phys. 2013, 15 (46), 20000–20004.

(25) Ji, L.; McDaniel, M. D.; Wang, S.; Posadas, A. B.; Li, X.; Huang, H.; Lee, J. C.; Demkov, A. A.; Bard, A. J.; Ekerdt, J. G.; et al. A Silicon-Based Photocathode for Water Reduction with an Epitaxial SrTiO3 Protection Layer and a Nanostructured Catalyst. Nat.

Nanotechnol. 2014, 10 (1), 84–90.

(26) Singh, R.; Green, M. A.; Rajkanan, K. Review of Conductor-Insulator-Semiconductor (CIS) Solar Cells. Sol. Cells 1981, 3 (2), 95–148.

(27) Dominey, R. N.; Lewis, N. S.; Bruce, J. A.; Bookbinder, D. C.; Wrighton, M. S. Improvement of Photoelectrochemical Hydrogen Generation by Surface Modification of P- Type Silicon Semiconductor Photocathodes. J. Am. Chem. Soc. 1982, 104, 467–482. (28) Szklarczyk, M.; Bockris, J. O. Photoelectrocatalysis and Electrocatalysis on P-Silicon. J.

118

Phys. Chem. 1984, 88, 1808–1815.

(29) Heller, A. Hydrogen-Evolving Solar Cells. Science 1984, 1141–1148.

(30) McCrory, C. C. L.; Jung, S.; Ferrer, I. M.; Chatman, S. M.; Peters, J. C.; Jaramillo, T. F. Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices. J. Am. Chem. Soc. 2015, 137 (13), 4347– 4357.

(31) Shao-Horn, Y.; Sheng, W. C.; Chen, S.; Ferreira, P. J.; Holby, E. F.; Morgan, D. Instability of Supported Platinum Nanoparticles in Low-Temperature Fuel Cells. Top. Catal. 2007, 46 (3–4), 285–305.

(32) Vesborg, P. C. K.; Jaramillo, T. F. Addressing the Terawatt Challenge: Scalability in the Supply of Chemical Elements for Renewable Energy. RSC Adv. 2012, 2 (21), 7933.

(33) Heller, A.; Aspnes, D. E.; Porter, J. D.; Sheng, T. T.; Vadimsky, R. G. Transparent Metals Preparation and Characterization of Light-Transmitting Platinum Films. J. Phys. Chem. 1985, 89 (1982), 4444–4452.

(34) Nakato, Y.; Ueda, K.; Yano, H.; Tsubomura, H. Effect of Microscopic Discontinuity of Metal Overlayers on the Photovoltages in Metal-Coated Semiconductor-Liquid Junction Photoelectrochemical Cells for Efficient Solar Energy. J. Phys. Chem. 1988, 92, 2316– 2324.

(35) Nakato, Y.; Tsubomura, H. Silicon Photoelectrodes Modified with Ultrafine Metal Islands.

Electrochim. Acta 1992, 897–907.

(36) Nakato, Y.; Yano, H.; Nishiura, S.; Ueda, T.; Tsubomura, H. Hydrogen Photoevolution at P-Type Silicon Electrodes Coated with Discontinous Metal Layers. J. Electroanal. Chem. 1987, 228, 97–108.

(37) Rossi, R. C.; Tan, M. X.; Lewis, N. S. Size-Dependent Electrical Behavior of Spatially Inhomogeneous Barrier Height Regions on Silicon. Appl. Phys. Lett. 2000, 77, 2698. (38) Oskam, G.; Long, J. G.; Natarajan, A.; Searson, P. C. Electrochemical Deposition of Metals

onto Silicon. J. Phys. D. Appl. Phys. 1998, 31, 1927–1949.

(39) Kawamura, Y. L.; Sakka, T.; Ogata, Y. H. Photoassisted Control of Pt Electrodeposition on P-Type Si. J. Electrochem. Soc. 2005, 152, C701.

(40) Aggour, M.; Skorupska, K.; Stempel Pereira, T.; Jungblut, H.; Grzanna, J.; Lewerenz, H. J. Photoactive Silicon-Based Nanostructure by Self-Organized Electrochemical Processing. J.

Electrochem. Soc. 2007, 154 (9), H794–H797.

(41) Liu, Y. H.; Gokcen, D.; Bertocci, U.; Moffat, T. P. Self-Terminating Growth of Platinum Films by Electrochemical Deposition. Science (80-. ). 2012, 338, 1327–1330.

119

(42) Arrington, D.; Curry, M.; Street, S.; Pattanaik, G.; Zangari, G. Copper Electrodeposition onto the Dendrimer-Modified Native Oxide of Silicon Substrates. Electrochim. Acta 2008,

53 (5), 2644–2649.

(43) Mirley, C.; Koberstein, J. A Room Temperature Method for the Preparation of Ultrathin SiOx Films from Langmuir-Blodgett Layers. Langmuir 1995, 11 (4), 1049–1052.

(44) Gould, T. D.; Izar, A.; Weimer, A. W.; Falconer, J. L.; Medlin, J. W. Stabilizing Ni Catalysts by Molecular Layer Deposition for Harsh, Dry Reforming Conditions. ACS Catal. 2014, 4 (8), 2714–2717.

(45) Joo, S. H.; Park, J. Y.; Tsung, C.-K.; Yamada, Y.; Yang, P.; Somorjai, G. A. Thermally Stable Pt/Mesoporous Silica Core-Shell Nanocatalysts for High-Temperature Reactions.

Nat. Mater. 2009, 8 (2), 126–131.

(46) Dai, Y.; Lim, B.; Yang, Y.; Cobley, C. M.; Li, W.; Cho, E. C.; Grayson, B.; Fanson, P. T.; Campbell, C. T.; Sun, Y.; et al. A Sinter-Resistant Catalytic System Based on Platinum Nanoparticles Supported on TiO2 Nanofibers and Covered by Porous Silica. Angew.

Chemie Int. Ed. 2010, 49 (44), 8165–8168.

(47) Takenaka, S.; Miyamoto, H.; Utsunomiya, Y.; Matsune, H.; Kishida, M. Catalytic Activity of Highly Durable Pt/CNT Catalysts Covered with Hydrophobic Silica Layers for the Oxygen Reduction Reaction in PEFCs. J. Phys. Chem. C 2014, 118 (2), 774–783.

(48) Maeda, K.; Teramura, K.; Lu, D.; Saito, N.; Inoue, Y.; Domen, K. Noble-Metal/Cr2O3 Core/Shell Nanoparticles as a Cocatalyst for Photocatalytic Overall Water Splitting. Angew.

Chemie Int. Ed. 2006, 45 (46), 7806–7809.

(49) Agiral, A.; Soo, H. Sen; Frei, H. Visible Light Induced Hole Transport from Sensitizer to Co 3 O 4 Water Oxidation Catalyst across Nanoscale Silica Barrier with Embedded Molecular Wires. Chem. Mater. 2013, 25 (11), 2264–2273.

(50) Mirley, C.; Koberstein, J. A Room Temperature Method for the Preparation of Ultrathin SiOx Films from Langmuir-Blodgett Layers. Langmuir 1995, 11 (4), 0–3.

(51) Phely-Bobin, T. S.; Muisener, R. J.; Koberstein, J. T.; Papadimitrakopoulos, F. Site-Specific Self-Assembly of Si/SiOx Nanoparticles on Micropatterned Poly(Dimethylsiloxane) Thin Films. Synth. Met. 2001, 116 (1–3), 439–443.

(52) Ouyang, M.; Yuan, C.; Muisener, R. J.; Boulares, A.; Koberstein, J. T. Conversion of Some Siloxane Polymers to Silicon Oxide by UV/Ozone Photochemical Processes. Chem. Mater. 2000, 12 (29), 1591–1596.

(53) Ustarroz, J.; Altantzis, T.; Hammons, J. a.; Hubin, A.; Bals, S.; Terryn, H. The Role of Nanocluster Aggregation, Coalescence, and Recrystallization in the Electrochemical Deposition of Platinum Nanostructures. Chem. Mater. 2014, 26 (7), 2396–2406.

120

(55) Daum, P. H.; Enke, C. G. Electrochemical Kinetics of the Ferri-Ferrocyanide Couple on Platinum. Anal. Chem. 1969, 41 (4), 653–656.

(56) Konopka, S. J.; McDuffie, B. Diffusion Coefficients of Ferri- and Ferrocyanide Ions in Aqueous Media, Using Twin-Electrode Thin-Layer Electrochemistry. Anal. Chem. 1970,

42 (14), 1741–1746.

(57) Scheuermann, A.; Kemp, K.; Tang, K.; Lu, D.; Satterthwaite, P.; Ito, T.; Chidsey, C. E. D.; Mc Intyre, P. Conductance and Capacitance of Bilayer Protective Oxides for Silicon Water Splitting Anodes. Energy Environ. Sci. 2015.

(58) Shewchun, J.; Singh, R.; Green, M. A. Theory of Metal-Insulator-Semiconductor Solar Cells. J. Appl. Phys. 1977, 48 (2), 765.

(59) Ouyang, M.; Muisener, R. .; Boulares, A.; Koberstein, J. . UV–ozone Induced Growth of a SiOx Surface Layer on a Cross-Linked Polysiloxane Film: Characterization and Gas Separation Properties. J. Memb. Sci. 2000, 177 (1–2), 177–187.

(60) Ouyang, M.; Klemchuk, P. P.; Koberstein, J. T. Exploring the Effectiveness of SiOx Coatings in Protecting Polymers against Photo-Oxidation. Polym. Degrad. Stab. 2000, 70 (2), 217–228.

(61) Velmurugan, J.; Zhan, D.; Mirkin, M. V. Electrochemistry through Glass. Nat. Chem. 2010,

2 (6), 498–502.

(62) Houston, K. S.; Weinkauf, D. H.; Stewart, F. F. Gas Transport Characteristics of Plasma Treated Poly(Dimethylsiloxane) and Polyphosphazene Membrane Materials. J. Memb. Sci. 2002, 205, 103–112.

(63) Green, M. A.; King, F. D.; Shewchun, J. Minority Carrier MIS Tunnel Diodes and Their Application to Electron-and Photo-Voltaic Energy Conversion—I. Theory. Solid. State.

Electron. 1974, 17, 551–561.

(64) Hezel, R. Recent Progress in {MIS} Solar Cells. Prog. Photovoltaics Res. Appl. 1997, 5 (November 1996), 109–120.

(65) Har-Lavan, R.; Ron, I.; Thieblemont, F.; Cahen, D. Toward Metal-Organic Insulator- Semiconductor Solar Cells, Based on Molecular Monolayer Self-Assembly on n-Si. Appl.

Phys. Lett. 2009, 94 (4), 043308.

(66) Kim, K. H.; Kim, H. J.; Jang, P.; Jung, C.; Seomoon, K. Properties of Low-Temperature Passivation of Silicon with ALD Al2O3 Films and Their PV Applications. Electron. Mater.

Lett. 2011, 7 (2), 171–174.

(67) Jung, Y.; Li, X.; Rajan, N. K.; Taylor, A. D.; Reed, M. a. Record High Efficiency Single- Walled Carbon Nanotube/Silicon p-n Junction Solar Cells. Nano Lett. 2013, 13, 95–99. (68) García De Arquer, F. P.; Mihi, A.; Kufer, D.; Konstantatos, G. Photoelectric Energy

121

Conversion of Plasmon-Generated Hot Carriers in Metal-Insulator-Semiconductor Structures. ACS Nano 2013, 7 (4), 3581–3588.

(69) Verwey, J. F.; Amerasekera, E. A.; Bisschop, J. The Physics of SiO2. Rep. Prog. Phys. 1990, 53, 1297–1331.

(70) Lee, J.-Y.; Lee, J. G.; Lee, S.; Seo, M.; Piao, L.; Bae, J. H.; Lim, S. Y.; Park, Y. J.; Chung, T. D. Hydrogen-Atom-Mediated Electrochemistry. Nat. Commun. 2013, 4 (May), 1–8. (71) Hattori, T.; Watanabe, K.; Ohashi, M.; Matsuda, M.; Yasutake, M. Electron Tunneling

through Chemical Oxide of Silicon. Appl. Surf. Sci. 1996, 102 (96), 86–89.

(72) Ustarroz, J.; Hammons, J. A.; Altantzis, T.; Hubin, A.; Bals, S.; Terryn, H. A Generalized Electrochemical Aggregative Growth Mechanism. J. Am. Chem. Soc. 2013, 135 (31), 11550–11561.

(73) Selvarajoo, T. A. L.; Ranjan, R.; Pey, K. L.; Tang, L. J.; Tung, C. H.; Lin, W. Dielectric- Breakdown-Induced Epitaxy: A Universal Breakdown Defect in Ultrathin Gate Dielectrics. In IEEE Trans. Electron Devices; 2005; Vol. 5, pp 190–197.

(74) Pey, K. L.; Tung, C. H.; Radhakrishnan, M. K.; Tang, L. J.; Lin, W. H. Dielectric Breakdown Induced Epitaxy in Ultrathin Gate Oxide - a Reliability Concern. Int. Electron

Devices Meet. 2002, 1 (C), 163–166.

(75) Azizi, N.; Yiannacouras, P. Gate Oxide Breakdown. ECE1768–Reliability Integr. Circuits 2003, 1–33.

(76) Lombardo, S.; Crupi, F.; La Magna, A.; Spinella, C.; Terrasi, A.; La Mantia, A.; Neri, B. Electrical and Thermal Transient during Dielectric Breakdown of Thin Oxides in Metal- SiO2-Silicon Capacitors. J. Appl. Phys. 1998, 84 (1), 472.

(77) Ranjan, R.; Pey, K. L.; Tung, C. H.; Tang, L. J.; Ang, D. S.; Groeseneken, G.; De Gendt, S.; Bera, L. K. Breakdown-Induced Thermochemical Reactions in HfO[Sub 2] High- κ/Polycrystalline Silicon Gate Stacks. Appl. Phys. Lett. 2005, 87 (24), 242907.

122

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