Anodic Oxidation of Tungsten under Illumination-Multi-Method Characterization and Modeling at the Molecular Level.

Tungsten oxide has received considerable attention as photo-anode in photo-assisted water splitting due to its considerable advantages such as significant light absorption in the visible region, good catalytic properties, and stability in acidic and oxidative conditions. The present paper is a first step in a detailed study of the mechanism of porous WO3 growth via anodic oxidation. In-situ electrochemical impedance spectroscopy (EIS) and intensity modulated photocurrent spectroscopy (IMPS) during oxidation of W illuminated with UV and visible light are employed to study the ionic and electronic processes in slightly acidic sulfate-fluoride electrolytes and a range of potentials 4-10 V. The respective responses are discussed in terms of the influence of fluoride addition on ionic and electronic process rates. A kinetic model is proposed and parameterized via regression of experimental data to the EIS and IMPS transfer functions.

BiVO4 Photoanode with NiV2O6 Back Contact Interfacial Layer for Improved Hole-Diffusion Length and Photoelectrochemical Water Oxidation Activity.

The short hole diffusion length (HDL) and high interfacial recombination are among the main drawbacks of semiconductor-based solar energy systems. Surface passivation and introducing an interfacial layer are recognized for enhancing HDL and charge carrier separation. Herein, we introduced a facile recipe to design a pinholes-free BiVO4 photoanode with a NiV2O6 back contact interfacial (BCI) layer, marking a significant advancement in the HDL and photoelectrochemical activity. The fabricated BiVO4 photoanode with NiV2O6 BCI layer exhibits a 2-fold increase in the HDL compared to pristine BiVO4. Despite this improvement, we found that the front surface recombination still hinders the water oxidation process, as revealed by photoelectrochemical (PEC) studies employing Na2SO3 electron donors and by intensity-modulated photocurrent spectroscopy measurements. To address this limitation, the surface of the NiV2O6/BiVO4 photoanode was passivated with a cobalt phosphate electrocatalyst, resulting in a dramatic enhancement in the PEC performance. The optimized photoanode achieved a stable photocurrent density of 4.8 mA cm-2 at 1.23 VRHE, which is 12-fold higher than that of the pristine BiVO4 photoanode. Density Functional Theory (DFT) simulations revealed an abrupt electrostatic potential transition at the NiV2O6/BiVO4 interface with BiVO4 being more negative than NiV2O6. A strong built-in electric field is thus generated at the interface and drifts photogenerated electrons toward the NiV2O6 BCI layer and photogenerated holes toward the BiVO4 top layer. As a result, the back-surface recombination is minimized, and ultimately, the HDL is extended in agreement with the experimental findings.

Revealing the enhanced photoelectrochemical water oxidation activity of Fe-based metal-organic polymer-modified BiVO4 photoanode.

Metal-organic polymers (MOPs) can enhance the photoelectrochemical (PEC) water oxidation performance of BiVO4 photoanodes, but their PEC mechanisms have yet to be comprehended. In this work, we constructed an active and stable composite photoelectrode by overlaying a uniform MOP on the BiVO4 surface using Fe2+ as the metal ions and 2,5-dihydroxyterephthalic acid (DHTA) as ligand. Such modification on the BiVO4 surface yielded a core-shell structure that could effectively enhance the PEC water oxidation activity of the BiVO4 photoanode. Our intensity-modulated photocurrent spectroscopy analysis revealed that the MOP overlayer could concurrently reduce the surface charge recombination rate constant (ksr) and enhance the charge transfer rate constant (ktr), thus accelerating water oxidation activity. These phenomena can be ascribed to the passivation of the surface that inhibits the recombination of the charge carrier and the MOP catalytic layer that improves the hole transfer. Our rate law analysis also demonstrated that the MOP coverage shifted the reaction order of the BiVO4 photoanode from the third-order to the first-order, resulting in a more favorable rate-determining step where only one hole accumulation is required to overcome water oxidation. This work provides new insights into the reaction mechanism of MOP-modified semiconductor photoanodes.

Intensity Modulated Photocurrent Microspectrosopy for Next Generation Photovoltaics.

In this report, a large-area laser beam induced current microscope that has been adapted to perform intensity modulated photocurrent spectroscopy (IMPS) in an imaging mode is described. Microscopy-based IMPS method provides a spatial resolution of the frequency domain response of the solar cell, allowing correlation of the optoelectronic response with a particular interface, bulk material, specific transport layer, or transport parameter. The system is applied to study degradation effects in back-contact perovskite cells where it is found to readily differentiate areas based on their markedly different frequency response. Using the diffusion-recombination model, the IMPS response is modeled for a sandwich structure and extended for the special case of lateral diffusion in a back-contact cell. In the low-frequency limit, the model is used to calculate spatial maps of the carrier ambipolar diffusion length. The observed frequency response of IMPS images is then discussed.

Electrodeposited Co-Substituted LaFeO3 for Enhancing the Photoelectrochemical Activity of BiVO4.

Co-substituted LaFeO3 was electrodeposited on the surface of BiVO4 as a co-catalyst to enhance the water splitting performance. Compared to bare BiVO4, the BiVO4/Co-LaFeO3 composite photoanode shows a water oxidation photocurrent of 3.4 mA/cm2 at 1.23 V versus reverse hydrogen electrode, accompanied by a notable cathodic shift in the onset potential for 300 mV. Combined optical and electrochemical characterizations show that the solid/electrolyte charge transfer efficiency of BiVO4 are dramatically improved by the incorporation of Co-substituted LaFeO3. From the surface kinetic study of charge carriers by intensity-modulated photocurrent spectroscopy, a suppressed surface recombination rate constant is observed and the enhanced photoelectrochemical water splitting performance observed in the BiVO4/Co-LaFeO3 photoanode is attributed to the surface passivation effect of Co-substituted LaFeO3.

Unveiling the Effects of Nanostructures and Core Materials on Charge-Transport Dynamics in Heterojunction Electrodes for Photoelectrochemical Water Splitting.

Understanding the photogenerated charge-transport dynamics of metal oxide electrodes is the key to providing a strategy for practical improvement in the photoelectrochemical reaction activity. Here, we analyze the electron transport of a 3D bicontinuous SnO2/BiVO4 nanostructured photoelectrode by intensity-modulated photocurrent spectroscopy. We compare this electrode with 3D WO3/BiVO4 and planar-type bilayer SnO2/BiVO4 electrodes. In the results, we observe an order of magnitude faster electron transport in the 3D electrodes relative to the bilayer electrode. Moreover, we observe trap-limited transport on widely applied WO3/BiVO4 electrodes but confirm rapid trap-free transport on 3D SnO2/BiVO4. We also characterize the effect of electron transport on the water-splitting reaction. The electron-transport rate is directly related to the charge-separation efficiency in the water-splitting reaction. The fast transport time of the 3D SnO2/BiVO4 leads to the achievement of a significantly higher charge separation efficiency of 94%.

Enhancing the Contact Area of Ti Wire as Photoanode Substrate of Flexible Fiber-Type Dye-Sensitized Solar Cells Using the TiO2 Nanotube Growth and Removal Technique.

The fiber-type dye-sensitized solar cell (FDSSC) with flexible and dim-light workable features is one of the promising energy generation devices for soft electronics. A novel TiO2 nanotube (TNT) growth and removal technique is proposed in this study to enhance the contact area of the Ti wire substrate using anodization and ultrasonication processes. Smaller and denser imprints of TNT on the surface of Ti wire are obtained when a smaller voltage was applied for anodization. The thickness of the TiO2 nanoparticle layer coated on the Ti wire is also optimized by varying the dip-coating layers. With the smallest diameter and densest distribution of TNT imprints on the Ti wire, the FDSSC with the TiO2/TNT-printed Ti wire photoanode, prepared using 30 V as the anodization voltage, shows the highest photon-to-electricity efficiency of 2.37% as a result of the rough surface of Ti wire substrate, which provides more contact, as well as the suitable thickness of the TiO2 nanoparticle layer, which promotes charge generation and transportation. The smallest charge-transfer resistance and the highest electron collection efficiency are also obtained in this case, as examined using the electrochemical impedance spectroscopy and intensity modulated photocurrent spectroscopy/intensity modulated photovoltage spectroscopy. This facile TNT growth and removal technique is expected to be able to be applied to other fields for enhancing the contact area of the titanium substrate and promoting the generation of electrochemical reactions.

Morphological Contributions to Interfacial Charge Trapping and Nongeminate Recombination in Polymer Solar Cells Revealed by UV Light Soaking.

Nongeminate charge recombination occurs over a broad range of time scales in polymer solar cells and represents a serious loss channel for the performance and lifetime of devices. Multiple factors influence this process, including changes in morphology and formation of permanent defects, but individual contributions are often difficult to resolve from conventional experiments. We use intensity modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS) to investigate nongeminate charge recombination in blends of poly[2,6-(4,4-bis-(2-ethylhexyl)-4 H-cyclopenta [2,1- b;3,4- b']dithiophene)- alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) solar cells. PCPDTBT/PCBM devices are exposed to varying doses of UV light resonant with PCBM to induce small perturbations in the thin film morphology, namely local heating. IMPS/IMVS sweeps display signatures unique to degradation, that is, photocurrent and photovoltage leading the excitation light modulation appearing as positive phase shifts or 1st quadrant features in Bode and Nyquist representations, respectively. We assign this component to interface charging at purified PCPDTBT/PCBM phase boundaries that trap mobile charges and facilitate nongeminate recombination. Time- and frequency-domain drift-diffusion simulations are then used to model the perturbed photocurrent responses that show good agreement with experiments. Trap occupancies and their impact of photocurrent production are investigated using variable background (dc) excitation light intensities revealing increases of the 1st quadrant component in devices irradiated for longer times. No evidence of chemical degradation was observed from molecular spectroscopy and imaging experiments, and we conclude that morphological changes are chiefly responsible for larger nongeminate charge recombination yields as devices age. Lastly, we propose that the 1st quadrant IMPS/IMVS is a universal signature of morphology-related degradation, although its relative contribution may vary between material systems.

Effect of Aging and PCBM Content on Bulk Heterojunction Organic Solar Cells Studied by Intensity Modulated Photocurrent Spectroscopy.

A series of encapsulated and nonencapsulated bulk heterojunction photovoltaic devices containing poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) with different P3HT:PCBM ratios were investigated using traditional steady-state as well as non-steady-state intensity modulated photocurrent spectroscopy (IMPS) techniques. The steady state J-V measurements showed that PCBM content did not have a significant effect on the efficiency for freshly prepared devices, whereas aged nonencapsulated devices exhibited a strong dependence on PCBM content. IMPS measurements showed a significant contribution of interfacial nongeminate recombination in nonencapsulated devices, which increased with decreasing PCBM content in the photoactive layer and cell aging. It was related to the formation of interfacial states at the P3HT/PCBM interface due to atmospheric contamination, which act as recombination centers. Device encapsulation was found to be effective in preventing the occurrence of interfacial recombination. Our results suggest that IMPS can be used as a diagnostic tool to predict the performance of bulk heterojunction organic solar cells. If a solar cell shows the presence of interfacial states as indicated by semicircle arcs in quadrant I of the IMPS complex plane plots, it is most likely that its performance will deteriorate with time due to enhanced interfacial recombination, even without further exposure to atmospheric contaminations. We conclude that interfacial nongeminate recombination is an important degradation mechanism in organic solar cells, especially in the case of exposure to atmospheric contaminants.