Photoselective Metal Deposition on Amorphous Silicon p-i-n Solar Cells\ud

A novel method is described for the patternwise metallization of amorphous silicon solar cells, based on photocathodic deposition. The electric field of the p-i-n structure is used for the separation of photogenerated charge carriers. The electrons are driven to the interface of the n+-layer with the solution where they reduce metal ions to metal. The large difference between the conductivity of dark and illuminated areas and the high sheet resistance of the n-type layer makes it possible to define a metal pattern by selective illumination. It is shown that both nickel and gold patterns can be deposited using this method. After annealing, an ohmic nickel contact is formed and the cell exhibits good photovoltaic characteristics

The GAP-TPC

Several experiments have been conducted worldwide, with the goal of observing low-energy nuclear recoils induced by WIMPs scattering off target nuclei in ultra-sensitive, low-background detectors. In the last few decades noble liquid detectors designed to search for dark matter in the form of WIMPs have been extremely successful in improving their sensitivities and setting the best limits. One of the crucial problems to be faced for the development of large size (multi ton-scale) liquid argon experiments is the lack of reliable and low background cryogenic PMTs: their intrinsic radioactivity, cost, and borderline performance at 87 K rule them out as a possible candidate for photosensors. We propose a brand new concept of liquid argon-based detector for direct dark matter search: the Geiger-mode Avalanche Photodiode Time Projection Chamber (GAP-TPC) optimized in terms of residual radioactivity of the photosensors, energy and spatial resolution, light and charge collection efficiencyComment: 7 pages, 5 figures, Accepted for publication on JINS

Competing charge transfer pathways at the photosystem II-electrode interface.

The integration of the water-oxidation enzyme photosystem II (PSII) into electrodes allows the electrons extracted from water oxidation to be harnessed for enzyme characterization and to drive novel endergonic reactions. However, PSII continues to underperform in integrated photoelectrochemical systems despite extensive optimization efforts. Here we carried out protein-film photoelectrochemistry using spinach and Thermosynechococcus elongatus PSII, and we identified a competing charge transfer pathway at the enzyme-electrode interface that short-circuits the known water-oxidation pathway. This undesirable pathway occurs as a result of photo-induced O2 reduction occurring at the chlorophyll pigments and is promoted by the embedment of PSII in an electron-conducting fullerene matrix, a common strategy for enzyme immobilization. Anaerobicity helps to recover the PSII photoresponse and unmasks the onset potentials relating to the QA/QB charge transfer process. These findings impart a fuller understanding of the charge transfer pathways within PSII and at photosystem-electrode interfaces, which will lead to more rational design of pigment-containing photoelectrodes in general.This work was supported by the U.K. Engineering and Physical Sciences Research Council (EP/H00338X/2 to E. Reisner), the U.K. Biology and Biotechnological Sciences Research Council (BB/K010220/1 to E. Reisner), a Marie Curie International Incoming Fellowship (PIIF-GA-2012-328085 RPSII to J.J.Z.). N.P. was supported by the Winton Fund for the Physics of Sustainability. E. Romero. and R.v.G. were supported by the VU University Amsterdam, the Laserlab-Europe Consortium, the TOP grant (700.58.305) from the Foundation of Chemical Sciences part of NWO, the Advanced Investigator grant (267333, PHOTPROT) from the European Research Council, and the EU FP7 project PAPETS (GA 323901). R.v.G. gratefully acknowledges his `Academy Professor' grant from the Royal Netherlands Academy of Arts and Sciences (KNAW). We would also like to thank Miss Katharina Brinkert and Prof A. William Rutherford for a sample of T. elongatus PSII, and H. v. Roon for preparation of the spinach PSII samples

La5Ti2Cu1-xAgxS5O7 photocathodes operating at positive potentials during photoelectrochemical hydrogen evolution under irradiation of up to 710 nm

A photoelectrochemical (PEC) cell based on a series-connected photocathode and photoanode made of particulate semiconductors is a potentially scalable and inexpensive device for renewable solar hydrogen production via PEC water splitting without any external power supply. The realisation of such PEC devices hinges on the development of photoelectrodes that operate at a small applied voltage. In this study, solid solutions of La5Ti2CuS5O7 (LTC) and La5Ti2AgS5O7 (LTA) were synthesised, and their physical, optical, and PEC properties in the water splitting reaction were discussed. LTC and LTA formed a La5Ti2Cu1-xAgxS5O7 solid solution (LTC(1-x)A(x)) over the whole compositional range. The indirect bandgap energy of LTC(1-x)A(x) changed nonlinearly with respect to composition, attaining its minimum value (ca. 1.8 eV) at a composition of x approximate to 0.16. Photoelectrodes of Al-doped LTC(1-x)A(x) solid solution powder fabricated using the particle transfer method exhibited a photocathodic response regardless of the Ag content. 1% Al-LTC(0.9)A(0.1) photocathodes exhibited the best PEC properties in the hydrogen evolution reaction and yielded a hypothetical half-cell solar-to-hydrogen energy conversion efficiency of 0.25% at +0.6 V vs. RHE, three times higher than the previously reported 1% Sc-LTC. In addition, 1% Al-LTC(0.9)A(0.1) photocathodes were fairly stable at + 0.7 V vs. RHE without any protective modifications. Owing to the positive operational electrode potential of 1% Al-LTC(0.9)A(0.1), unassisted PEC water splitting was accomplished using series-connected photoelectrodes made of 1% Al-LTC(0.9)A(0.1) and BaTaO2N, particulate semiconductors with absorption edge wavelengths of 710 and 660 nm, respectively, at a Faradaic efficiency of unity and a solar-to-hydrogen energy conversion efficiency of approximately 0.1%.ArticleEnergy & Environmental Science.8(11):3354-3362(2015)journal articl

Combinatorial synthesis and high-throughput photopotential and photocurrent screening of mixed-metal oxides for photoelectrochemical water splitting

A high-throughput method has been developed using a commercial piezoelectric inkjet printer for synthesis and characterization of mixed-metal oxide photoelectrode materials for water splitting. The printer was used to deposit metal nitrate solutions onto a conductive glass substrate. The deposited metal nitrate solutions were then pyrolyzed to yield mixed-metal oxides that contained up to eight distinct metals. The stoichiometry of the metal oxides was controlled quantitatively, allowing for the creation of vast libraries of novel materials. Automated methods were developed to measure the open-circuit potentials (Eoc), short-circuit photocurrent densities (Jsc), and current density vs. applied potential (J–E) behavior under visible light irradiation. The high-throughput measurement of Eoc is particularly significant because open-circuit potential measurements allow the interfacial energetics to be probed regardless of whether the band edges of the materials of concern are above, close to, or below the values needed to sustain water electrolysis under standard conditions. The Eoc measurements allow high-throughput compilation of a suite of data that can be associated with the composition of the various materials in the library, to thereby aid in the development of additional screens and to form a basis for development of theoretical guidance in the prediction of additional potentially promising photoelectrode compositions

Insight on Shallow Trap States-Introduced Photocathodic Performance in n-Type Polymer Photocatalysts

Graphitic carbon nitride (g-C3N4) is a robust organic semiconductor photocatalyst with proven H2 evolution ability. However, its application in a photoelectrochemical system as a photocathode for H2 production is extremely challenging with the majority of reports representing it as a photoanode. Despite research into constructing g-C3N4 photocathodes in recent years, factors affecting an n-type semiconductor’s properties as a photocathode are still not well-understood. The current work demonstrates an effective strategy to transform an n-type g-C3N4 photoanode material into an efficient photocathode through introducing electron trap states associated with both N-defects and C–OH terminal groups. As compared to the g-C3N4 photoelectrode, this strategy develops 2 orders of magnitude higher conductivity and 3 orders of magnitude longer-lived shallow-trapped charges. Furthermore, the average OCVD lifetime observed for def-g-C3N4 is 5 times longer than that observed for g-C3N4. Thus, clear photocathode behavior has been observed with negative photocurrent densities of around −10 μA/cm2 at 0 V vs RHE. Open circuit photovoltage decay (OCVD), Mott–Schottky (MS) plot, and transient absorption spectroscopy (TAS) provide consistent evidence that long-lived shallow-trapped electrons that exist at about the microsecond time scale after photoexcitation are key to the photocathode behavior observed for defect-rich g-C3N4, thus further demonstrating g-C3N4 can be both a photoanode and a photocathode candidate

Micromixing-assisted Fabrication and Photoelectrochemical Performance Investigation of TiO2 Photoanodes with Visible Light Response

基于TiO2半导体特殊的光电化学性能，其有望成为绿色、环保的新型金属防腐技术中最为重要的光阳极材料。但是，TiO2存在可见光利用率低、光量子效率不高等限制其实际应用的问题。此外，由于传统混合方式在快速沉淀体系中难以有效调控均相化学过程，导致碱性液相环境制备有序TiO2薄膜至今仍无法实现。基于上述考虑，本论文提出使用微混合设备辅助在碱性液相环境下制备出形貌可控的TiO2薄膜光阳极，并通过沉淀剂对产物进行选择性原位掺杂改性。通过数值模拟及实验测试深入研究了制备条件和掺杂对TiO2薄膜光阳极光电化学性能的影响。本论文的主要研究内容和结果如下： 1、基于自行设计并制造的多孔分散微结构混合器，对液-液...TiO2 semiconductor is expected as the most important photoanode material applied for the novel green and environmental friendly metal anticorrosion technology, because of its unique photoelectrochemical properties. Nevertheless, the inherent disadvantages of the TiO2, lies in their limited visible light utilization and quantum yield, have extremely restricted their practical applications. Moreover...学位：工学博士院系专业：材料学院_材料学学号：2072010015347

A tool box to ascertain the nature of doping and photoresponse in single-walled carbon nanotubes

The effect of doping on the electronic properties in bulk single-walled carbon nanotube (SWCNT) samples is studied for the first time using a new in situ Raman spectroelectrochemical method, and further verified by DFT calculations and photoresponse. We use p-/n-doped SWCNTs prepared by diazonium reactions as a versatile chemical strategy to control the SWCNT behavior. The measured and calculated data testify an acceptor effect of 4-aminobenzenesulfonic acid (p-doping), and a donor effect (n-doping) in the case of benzyl alcohol. In addition, pristine and covalently functionalized SWCNTs were used for the preparation of photoactive film electrodes. The photocathodic current in the photoelectrochemical cell is consistently modulated by the doping group. These results validate the in situ Raman spectroelectrochemistry as a unique tool box for predicting the electronic properties of functionalized SWCNTs in the form of thin films and their operational functionality in thin film devices for future optoelectronic applications

Light-Triggered Electron Transfer between a Conjugated Polymer and Cytochrome C for Optical Modulation of Redox Signaling

Protein reduction/oxidation processes trigger and finely regulate a myriad of physiological and pathological cellular functions. Many biochemical and biophysical stimuli have been recently explored to precisely and effectively modulate intracellular redox signaling, due to the considerable therapeutic potential. Here, we propose a first step toward an approach based on visible light excitation of a thiophene-based semiconducting polymer (P3HT), demonstrating the realization of a hybrid interface with the Cytochrome c protein (CytC), in an extracellular environment. By means of scanning electrochemical microscopy and spectro-electrochemistry measurements, we demonstrate that, upon optical stimulation, a functional interaction between P3HT and CytC is established. Polymer optical excitation locally triggers photoelectrochemical reactions, leading to modulation of CytC redox activity, either through an intermediate step, involving reactive oxygen species formation, or via a direct photoreduction process. Both processes are triggered by light, thus allowing excellent spatiotemporal resolution, paving the way to precise modulation of protein redox signaling