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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Wafer-scale two-dimensional Au-TiO{sub 2} bilayer films for photocatalytic degradation of Palmitic acid under UV and visible light illumination

Highlights: • Successful wafer-scale atomic layer deposition of 2D Au-TiO{sub 2} bilayer photocatalyst films. • The efficient degradation of fatty acid by tailoring 2D TiO{sub 2} films under UV and visible light illumination. • Improved visible light photocatalytic activity and photocurrent density of 2D Au-TiO{sub 2} bilayer films. • Comparable photocatalytic performance of ultra-thin 2D TiO{sub 2} and thick TiO{sub 2} films under UV light illumination. - Abstract: Bilayer Au-TiO{sub 2} configuration with two-dimensional (2D) TiO{sub 2} films enabled sensible improvement in photocatalytic degradation of Palmitic Acid (PA) and also the enhancement of current density under visible light illumination. The improved visible light photocatalytic and photocurrent properties were attained when 35 nm thick 2D TiO{sub 2} film was developed by atomic layer deposition (ALD) on Si/SiO{sub 2}-Au substrate. The Au-TiO{sub 2} bilayer demonstrated the improved photocatalytic and photovoltaic performances compared with those TiO{sub 2} films developed on Si/SiO{sub 2} bare substrate. These improvements can be attributed to the plasmonic effects of Au film acting as antenna for visible light and also serving as hole acceptor during photocatalysis process. The proposed mechanisms for enhanced visible light performance of bilayer films are hot electron injection and the formation of hot spots at Au-TiO{sub 2} interface which contributed to the electron injection to conduction band of TiO{sub 2} or facilitated the separation of generated electron-hole pairs at Au-TiO{sub 2} Schottky junction.

36 MATERIALS SCIENCE↗
DOE OSTI2018

An In 0.42 Ga 0.58 N tunnel junction nanowire photocathode monolithically integrated on a nonplanar Si wafer

Group III-nitride semiconductors exhibit many ideal characteristics for solar water splitting, including a tunable energy bandgap across nearly the entire solar spectrum and suitable band edge positions for water oxidation and proton reduction under visible and near-infrared light irradiation. To date, however, the best reported energy conversion efficiency for III-nitride semiconductor photocathodes is still below 1%. Here we report on the demonstration of a relatively efficient p-type In 0.42 Ga 0.58 N photocathode, which is monolithically integrated on an n-type nonplanar Si wafer through a GaN nanowire tunnel junction. The open pillar design, together with the nonplanar Si wafer can significantly maximize light trapping, whereas the tunnel junction reduces the interfacial resistance and enhances the extraction of photo-generated electrons. In addition, photodeposited Pt nanoparticles on InGaN nanowire surfaces significantly improve the cathodic performance. The nanowire photocathode exhibits a photocurrent density of 12.3 mA cm -2 at 0 V vs. RHE and an onset potential of 0.79 V vs. RHE under AM 1.5G one-sun illumination. Here, the maximum applied bias photon-to-current efficiency reaches 4% at ~0.52 V vs. RHE, which is one order of magnitude higher than the previously reported values for III-nitride photocathodes. Significantly, no performance degradation was measured for over 30 hours solar water splitting with a steady photocurrent density ~12 mA cm -2 without using any extra surface protection, which is attributed to the spontaneous formation of N-terminated surfaces of InGaN nanowires to protect against photocorrosion.

42 ENGINEERING↗
DOE OSTI2019

Highly efficient and stable p-type ZnO nanowires with piezotronic effect for photoelectrochemical water splitting

Unremitting efforts have been made to develop high-performance photoelectrochemical (PEC) water-splitting system to produce clean hydrogen fuel using sunlight. In this research, a novel way, combining highly-ordered nanowires (NWs) structure and piezotronic effect of p-type ZnO has been demonstrated to dramatically enhance PEC hydrogen evolution performance. Systematic characterizations indicate that the Sb atoms uniformly dope into ZnO NWs and substitute Zn sites with the introduction of two zinc vacancies to form the shallow acceptor Sb Zn –2V Zn complex. Detailed synchrotron-based X-ray absorption near-edge structure (XANES) experiments in O K-edge and Zn L-edge further confirm the formation of the complex, and theoretical calculation verifies the Sb 5+ state dominating the complex. The optimal photocurrent density of the 0.2Sb/ZnO-anneal NWs can reach –0.85 mA/cm 2 (0 V RHE ) which is 17.2 times larger than that of the n-ZnO NWs under sunlight illumination (100 mW/cm 2 ). Furthermore, the piezotronic effect can be introduced to regulate the charge separation and transfer in the ZnO NWs through modulating the band structure near the interface. The photocurrent density can further increase to –1.08 mA/cm 2 (0 V RHE ) under a 0.6% tensile strain, which is 27.4% enhancement with respect to the ZnO sample without strain. These conclusions provide an efficient way to design and develop high-performance photoelectrodes toward PEC hydrogen evolution.

08 HYDROGEN↗
DOE OSTI2018

Advanced light trapping scheme in decoupled front and rear textured thin-film silicon solar cells

In this paper we present the study of an advanced light trapping scheme applied to thin-film silicon-based solar cells, overcoming the broadband Green absorption limit, that is the generalized case of the 4n 2 classical absorption limit for all wavelengths. This result is achieved by the 3-dimensional optical modelling of a fully functional thin-film hydrogenated nano-crystalline silicon (nc-Si:H) solar cell endowed with decoupled front and back textures. Our results stem from rigorously characterized optical properties of state-of-the-art materials, optimized geometric nano-features on the front and rear surfaces of the solar cell, and thickness optimization of the front transparent oxide. The simulated improvements derive from a gain in light absorption, especially in the near-infrared part of the spectrum close to the band gap of nc-Si:H. In this wavelength region, the material is weakly absorbing, whereas we now find significant absorptance peaks that can only be explained by the concurrent excitation of guided resonances by front and rear textures. This insight indicates the need to modify the temporal coupled-mode theory, which fails to predict the absorption enhancement achieved in this work, extending its validity to the case of decoupled front/back texturing. Our approach results in substantially high photocurrent density (>36 mA/cm 2 ), creating a platform suitable for high efficiency single and multi-junction thin-film solar cells based either on typical silicon alloys or on the novel and promising barium (di)silicide (BaSi2) absorber. In the latter case, using the same advanced light trapping employed for nc-Si:H, we demonstrate a very high implied photocurrent density of 41.1 mA/cm 2 , for a device endowed with 2-μm thick absorber.

14 SOLAR ENERGY↗
DOE OSTI2020

Combined Experimental and Theoretical Investigations of n-Type BiFeO 3 for Use as a Photoanode in a Photoelectrochemical Cell

Combined experimental and theoretical investigations were performed to evaluate the potential of n-type BiFeO 3 as a photoanode. While previous experimental and theoretical studies on BiFeO 3 mainly focused on its ferroelectric properties, several studies have reported the advantages of BiFeO 3 as a photoelectrode for solar water splitting (e.g. bandgap energy and band edge positions relative to water reduction and oxidation potentials). However, the photoelectrochemical properties of n-type BiFeO 3 have not yet been thoroughly investigated. In our experimental investigation, we developed an electrodeposition-based synthesis to prepare uniform n-type BiFeO 3 thin-film electrodes. Furthermore, using a heat treatment under a N 2 environment, we intentionally introduced additional oxygen vacancies into the pristine n-type BiFeO 3 electrodes to increase the majority carrier density. The bandgaps, flatband potentials, photocurrent onset potentials, photocurrent generation, and photoelectrochemical stabilities of the pristine and N 2 -treated BiFeO 3 photoanodes were investigated comparatively to improve our understanding of BiFeO 3 photoanodes and to examine the effect of oxygen vacancies on the photoelectrochemical properties of BiFeO 3 . In our theoretical investigation, we performed first-principles calculations and demonstrated the formation of a small polaron when an extra electron was introduced into the BiFeO 3 lattice. Changes in electronic states cause by the small polaron formation were carefully investigated. We also examined the effects of oxygen vacancies on electron polaron formation and carrier concentration in BiFeO 3 . Using charge formation energy calculations and referencing charge transition levels to the free electron polaron level instead of to the conduction band minimum, we showed that the oxygen vacancy is capable of serving as a donor to enhance the carrier concentration of BiFeO 3 . Furthermore, our theoretical results agree well with our experimental findings. Together, the new experimental and theoretical results and discussion provided in this study have considerably improved our understanding of n-type BiFeO 3 as a photoanode.

25 ENERGY STORAGE↗
DOE OSTI2023

Investigation of Electron Extraction and Protection Layers on Cu 2 O Photocathodes

Many semiconductor photoelectrodes used for solar fuel production require the addition of buffer and protection layers to enhance their solar-to-fuel conversion efficiency and long-term stability. For example, Cu 2 O, which is the most efficient oxide-based photocathode but suffers from photocorrosion, has been assembled with various buffer and protection layers to suppress photocorrosion and use more photoexcited electrons for useful reactions such as water reduction to H 2 . However, the abilities of various buffer and protection layers to extract electrons from Cu 2 O have never been directly evaluated. Instead, their abilities were estimated based on the photocurrent for water reduction after adding a hydrogen evolution catalyst on top of them. In these evaluations, as the photocurrent is affected not only by the buffer or protection layer but also by the catalyst, the ability of the buffer or protection layer to extract electrons from Cu 2 O could not be accurately determined or compared. Here, in this study, we demonstrate that 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL), whose reduction rate is faster than the photocorrosion rate of Cu 2 O, can be used as an effective electron scavenger to directly evaluate any change caused by a buffer or protection layer in electron-hole separation in Cu 2 O. In particular, we compared the performances of ZnO and TiO 2 layers on Cu 2 O for extracting electrons and suppressing photocorrosion. We also compared the performances of TiO 2 layers prepared by electrodeposition and atomic layer deposition (ALD) to show that the deposition method can make a striking impact on the performance of the same TiO 2 because it can affect the critical characteristics of the layer (e.g., defect levels, conductivity, interfacial atomic arrangements) that govern interfacial charge transfer in multilayer photoelectrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2015

TlHgInS 3 : An Indirect-Band-Gap Semiconductor with X-ray Photoconductivity Response

The quaternary compound TlHgInS3 crystallizes in a new structure type of space group, C2/c, with cell parameters a = 13.916(3) angstrom, b = 3.9132(8) angstrom, c = 21.403(4) angstrom, beta = 104.16(3)degrees, V = 1130.1(8) angstrom(3), and rho = 7.241 g/cm(3). The structure is a unique three-dimensional framework with parallel tunnels, which is formed by (1)(infinity)[InS33-] infinite chains bridged by linearly coordinated Hg2+ ions. TlHgInS3 is a semiconductor with a band gap of 1.74 eV and a resistivity of similar to 4.32 G Omega cm. TlHgInS3 single crystals exhibit photocurrent response when exposed to Ag X-rays. The mobility-lifetime product (mu tau) of the electrons and holes estimated from the photocurrent measurements are (mu tau)(e) approximate to 3.6 x 10(-4) cm(2)/V and (mu tau)(h) approximate to 2.0 x 10(-4) cm(2)/V. Electronic structure calculations at the density functional theory level indicate an indirect band gap and a relatively small effective mass for both electrons and holes. Based on the photoconductivity data, TlHgInS3 is a potential material for radiation detection applications.

Li, Hao↗
DOE OSTI2016

Increased Optoelectronic Quality and Uniformity of Hydrogenated p-InP Thin Films

The thin-film vapor-liquid-solid (TF-VLS) growth technique presents a promising route for high quality, scalable, and cost-effective InP thin films for optoelectronic devices. Toward this goal, careful optimization of material properties and device performance is of utmost interest. Here, we show that exposure of polycrystalline Zn-doped TF-VLS InP to a hydrogen plasma (in the following referred to as hydrogenation) results in improved optoelectronic quality as well as lateral optoelectronic uniformity. A combination of low temperature photoluminescence and transient photocurrent spectroscopy was used to analyze the energy position and relative density of defect states before and after hydrogenation. Notably, hydrogenation reduces the relative intragap defect density by 1 order of magnitude. As a metric to monitor lateral optoelectronic uniformity of polycrystalline TF-VLS InP, photoluminescence and electron beam induced current mapping reveal homogenization of the grain versus grain boundary upon hydrogenation. At the device level, we measured more than 260 TF-VLS InP solar cells before and after hydrogenation to verify the improved optoelectronic properties. Hydrogenation increased the average open-circuit voltage (VOC) of individual TF-VLS InP solar cells by up to 130 mV and reduced the variance in VOC for the analyzed devices.

14 SOLAR ENERGY↗
DOE OSTI2017

Improved Stability and Performance of Visible Photoelectrochemical Water Splitting on Solution-Processed Organic Semiconductor Thin Films by Ultrathin Metal Oxide Passivation

Solution-processable organic semiconductors have potentials as visible photoelectrochemical (PEC) water splitting photoelectrodes due to their tunable small band gap and electronic energy levels, but they are typically limited by poor stability and photocatalytic activity. In this study, we demonstrate the direct visible PEC water oxidation on solution-processed organic semiconductor thin films with improved stability and performance by ultrathin metal oxide passivation layers. N-type fullerene-derivative thin films passivated by sub-2 nm ZnO via atomic layer deposition enabled the visible PEC water oxidation at wavelengths longer than 600 nm in harsh alkaline electrolyte environments with up to 30 μA/cm 2 photocurrents at the thermodynamic water-oxidation equilibrium potential and the photoanode half-lifetime extended to ~1000 s. The systematic investigation reveals the enhanced water oxidation catalytic activity afforded by ZnO passivation and the charge tunneling governing the hole transfer through passivation layers. Further enhanced PEC performances were realized by improving the bottom ohmic contact to the organic semiconductor, achieving ~60 μA/cm 2 water oxidation photocurrent at the equilibrium potential, the highest values reported for organic semiconductor thin films to our knowledge. The improved stability and performance of passivated organic photoelectrodes and discovered design rationales provide useful guidelines for realizing the stable visible solar PEC water splitting based on organic semiconductor thin films.

14 SOLAR ENERGY↗
DOE OSTI2017

Investigation of Pristine and (Mo, W)-Doped Cu 11 V 6 O 26 for Use as Photoanodes for Solar Water Splitting

The development of new and inexpensive semiconductor electrodes that possess suitable bandgap energies and band positions for solar water splitting is of great interest in the field of solar fuel production. In this study, n-type Cu 11 V 6 O 26 that has a bandgap energy of 1.9 eV was produced as a pure, high quality photoanode and its properties and stability for photoelectrochemical water splitting were systematically investigated in pH 9.2 and pH 13 solutions. As Cu 11 V 6 O 26 photoanodes appeared to suffer from poor charge transport properties, Mo and W-doping into the V site were also examined, which considerably improved the photocurrent generation of Cu 11 V 6 O 26 . Furthermore, the bandgap energy, band edge positions, flatband potential, photocurrent generation, and photostability of pristine and doped Cu 11 V 6 O 26 electrodes are discussed in comparison to elucidate the effect of Mo- and W-doping and to evaluate the promise and limitations of Cu 11 V 6 O 26 as a photoanode for use in a water splitting photoelectrochemical cell.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Undoped and Ni-doped CoO x surface modification of porous BiVO 4 photoelectrodes for water oxidation

Surface modification of photoanodes with oxygen evolution reaction (OER) catalysts is an effective approach to enhance water oxidation kinetics, to reduce external bias, and to improve the energy harvesting efficiency of photoelectrochemical (PEC) water oxidation. Here, the surface of porous BiVO 4 photoanodes was modified by the deposition of undoped and Ni-doped CoO x via nitrogen flow assisted electrostatic spray pyrolysis. This newly developed atmospheric pressure deposition technique allows for surface coverage throughout the porous structure with thickness and composition control. PEC testing of modified BiVO 4 photoanodes shows that after deposition of an undoped CoO x surface layer, the onset potential shifts negatively by ca. 420 mV and the photocurrent density reaches 2.01 mA cm –2 at 1.23 vs V RHE under AM 1.5G illumination. Modification with Ni-doped CoO x produces even more effective OER catalysis and yields a photocurrent density of 2.62 mA cm –2 at 1.23 V RHE under AM 1.5G illumination. Furthermore, the valence band X-ray photoelectron spectroscopy and synchrotron-based X-ray absorption spectroscopy results show the Ni doping reduces the Fermi level of the CoO x layer; the increased surface band bending produced by this effect is partially responsible for the superior PEC performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

MOF-Sensitized Solar Cells Enabled by a Pillared Porphyrin Framework

Metal–organic frameworks (MOFs) are highly ordered, functionally tunable supramolecular materials with the potential to improve dye-sensitized solar cells (DSSCs). Several recent reports have indicated that photocurrent can be generated in Grätzel-type DSSC devices when MOFs are used as the sensitizer. However, the specific role(s) of the incorporated MOFs and the potential influence of residual MOF precursor species on device performance are unclear. Herein, we describe the assembly and characterization of a simplified DSSC platform in which isolated MOF crystals are used as the sensitizer in a planar device architecture. We selected a pillared porphyrin framework (PPF) as the MOF sensitizer, taking particular care to avoid contamination from light-absorbing MOF precursors. Photovoltaic and electrochemical characterization under simulated 1-sun and wavelength-selective illumination revealed photocurrent generation that is clearly ascribable to the PPF MOF. In conclusion, continued refinement of highly versatile MOF structure and chemistry holds promise for dramatic improvements in emerging photovoltaic technologies.

14 SOLAR ENERGY↗
DOE OSTI2018

Pressure Impact on the Crystal Structure, Optical, and Transport Properties in Layered Oxychalcogenides BiCu Ch O( Ch = S, Se)

The layered oxychalcogenides BiCuChO (Ch = S, Se, Te) represent a unique family of two-dimensional semiconductors with extraordinary optoelectronic and thermoelectric properties. Chemical strategies such as elemental doping have been used to modify their crystal structures and electronic configurations for better photocatalytic performances. Herein, we report the pressure impact on the crystalline and electronic band structures of BiCuChO (Ch = S, Se) with in situ synchrotron X-ray diffraction, Raman spectroscopy, electric resistivity and photocurrent measurements, and first-principle calculations. Under pressure, the crystalline lattices shrink continuously without symmetry breaking, which enhances the crystal field splitting; on the other hand, the pressure-induced charge delocalization causes the band broadening. The competition between the crystal field and charge delocalization demonstrates an efficient tool for band gap engineering: the electrical conductivity is enhanced below 12 GPa and monotonically decreases up to 40 GPa. In addition, BiCuSeO exhibits considerable photocurrent up to ~40 GPa, which suggests its potential application in pressure-responsive optoelectrical devices. Lastly, the comprehensive studies of the pressure effect on the crystal structure and electronic properties in two-dimensional semiconductors provide and in-depth understanding for developing new optoelectronic materials under extreme conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Electronic Coherence and Coherent Dephasing in the Optical Control of Electrons in Graphene

Electronic coherence is of utmost importance for the access and control of quantum-mechanical solid-state properties. Using a purely electronic observable, the photocurrent, we measure a lower bound of the electronic coherence time of 22 ± 4 fs in graphene. The photocurrent is ideally suited to measure electronic coherence, as it is a direct result of coherent quantum-path interference, controlled by the delay between two ultrashort two-color laser pulses. The maximum delay for which interference between the population amplitude injected by the first pulse interferes with that generated by the second pulse determines the electronic coherence time. In particular, numerical simulations reveal that the experimental data yields a lower bound on the electronic coherence time, masked by coherent dephasing due to the broadband absorption in graphene. Overall, we expect that our results will significantly advance the understanding of coherent quantum control in solid-state systems ranging from excitation with weak fields to strongly driven systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

3D Band Diagram and Photoexcitation of 2D–3D Semiconductor Heterojunctions

The emergence of a rich variety of two-dimensional (2D) layered semiconductor materials has enabled the creation of atomically thin heterojunction devices. Junctions between atomically thin 2D layers and 3D bulk semiconductors can lead to junctions that are fundamentally electronically different from the covalently bonded conventional semiconductor junctions. In this paper, we propose a new 3D band diagram for the heterojunction formed between n-type monolayer MoS 2 and p-type Si, in which the conduction and valence band-edges of the MoS 2 monolayer are drawn for both stacked and in-plane directions. This new band diagram helps visualize the flow of charge carriers inside the device in a 3D manner. Our detailed wavelength-dependent photocurrent measurements fully support the diagrams and unambiguously show that the band alignment is type I for this 2D-3D heterojunction. Photogenerated electron–hole pairs in the atomically thin monolayer are separated and driven by an external bias and control the “on/off” states of the junction photodetector device. Finally, two photoresponse regimes with fast and slow relaxation are also revealed in time-resolved photocurrent measurements, suggesting the important role played by charge trap states.

36 MATERIALS SCIENCE↗
DOE OSTI2015

High-Responsivity Graphene–Boron Nitride Photodetector and Autocorrelator in a Silicon Photonic Integrated Circuit

Graphene and other two-dimensional (2D) materials have emerged as promising materials for broadband and ultrafast photodetection and optical modulation. These optoelectronic capabilities can augment complementary metal–oxide–semiconductor (CMOS) devices for high-speed and low-power optical interconnects. We demonstrate an on-chip ultrafast photodetector based on a two-dimensional heterostructure consisting of high-quality graphene encapsulated in hexagonal boron nitride. Coupled to the optical mode of a silicon waveguide, this 2D heterostructure-based photodetector exhibits a maximum responsivity of 0.36 A/W and high-speed operation with a 3 dB cutoff at 42 GHz. From photocurrent measurements as a function of the top-gate and source-drain voltages, we conclude that the photoresponse is consistent with hot electron mediated effects. At moderate peak powers above 50 mW, we observe a saturating photocurrent consistent with the mechanisms of electron–phonon supercollision cooling. This nonlinear photoresponse enables optical on-chip autocorrelation measurements with picosecond-scale timing resolution and exceptionally low peak powers.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Interlayer exciton optoelectronics in a 2D heterostructure p–n junction

Semiconductor heterostructures are backbones for solid-state-based optoelectronic devices. Recent advances in assembly techniques for van der Waals heterostructures have enabled the band engineering of semiconductor heterojunctions for atomically thin optoelectronic devices. In two-dimensional heterostructures with type II band alignment, interlayer excitons, where Coulomb bound electrons and holes are confined to opposite layers, have shown promising properties for novel excitonic devices, including a large binding energy, micron-scale in-plane drift-diffusion, and a long population and valley polarization lifetime. Here, we demonstrate interlayer exciton optoelectronics based on electrostatically defined lateral p–n junctions in a MoSe 2 –WSe 2 heterobilayer. Applying a forward bias enables the first observation of electroluminescence from interlayer excitons. At zero bias, the p–n junction functions as a highly sensitive photodetector, where the wavelength-dependent photocurrent measurement allows the direct observation of resonant optical excitation of the interlayer exciton. The resulting photocurrent amplitude from the interlayer exciton is about 200 times smaller than the resonant excitation of intralayer exciton. This implies that the interlayer exciton oscillator strength is 2 orders of magnitude smaller than that of the intralayer exciton due to the spatial separation of electron and hole to the opposite layers. Lastly, these results lay the foundation for exploiting the interlayer exciton in future 2D heterostructure optoelectronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2017

All-in-One Derivatized Tandem p + n-Silicon–SnO 2 /TiO 2 Water Splitting Photoelectrochemical Cell

Mesoporous metal oxide film electrodes consisting of derivatized 5.5 μm thick SnO 2 films with an outer 4.3 nm shell of TiO 2 added by atomic layer deposition (ALD) have been investigated to explore unbiased water splitting on p, n, and p + n type silicon substrates. Modified electrodes were derivatized by addition of the water oxidation catalyst, [Ru(bda)(4-O(CH 2 ) 3 PO 3 H 2 )-pyr) 2 ], 1, (pyr = pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate), and chromophore, [Ru(4,4'-PO 3 H 2 -bpy) (bpy) 2 ] 2+ , RuP2+, (bpy = 2,2'-bipyridine), which form 2:1 RuP 2+ /1 assemblies on the surface. At pH 5.7 in 0.1 M acetate buffer, these electrodes with a fluorine-doped tin oxide (FTO) back contact under ~1 sun illumination (100 mW/cm 2 ; white light source) perform efficient water oxidation with a photocurrent of 1.5 mA/cm2 with an 88% Faradaic efficiency (FE) for O 2 production at an applied bias of 600 mV versus RHE ( ACS Energy Lett., 2016, 1, 231-236). The SnO 2 /TiO 2 –chromophore–catalyst assembly was integrated with the Si electrodes by a thin layer of titanium followed by an amorphous TiO 2 (Ti/a-TiO 2 ) coating as an interconnect. In the integrated electrode, p + n-Si–Ti/a-TiO 2 –SnO2/TiO 2 |-2RuP 2+ /1, the p+n-Si junction provided about 350 mV in added potential to the half cell. In photolysis experiments at pH 5.7 in 0.1 M acetate buffer, bias-free photocurrents approaching 100 μA/cm 2 were obtained for water splitting, 2H 2 O → 2H 2 + O 2 . The FE for water oxidation was 79% with a hydrogen efficiency of ~100% at the Pt cathode.

14 SOLAR ENERGY↗