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At least 73 records · Page 4

Evaluation of Parallel-Element, Variable-Impedance, Broadband Acoustic Liner Concepts

Recent trends in aircraft engine design have highlighted the need for acoustic liners that provide broadband sound absorption with reduced liner thickness. Three such liner concepts are evaluated using the NASA normal incidence tube. Two concepts employ additive manufacturing techniques to fabricate liners with variable chamber depths. The first relies on scrubbing losses within narrow chambers to provide acoustic resistance necessary for sound absorption. The second employs wide chambers that provide minimal resistance, and relies on a perforated sheet to provide acoustic resistance. The variable-depth chambers used in both concepts result in reactance spectra near zero. The third liner concept employs mesh-caps (resistive sheets) embedded at variable depths within adjacent honeycomb chambers to achieve a desired impedance spectrum. Each of these liner concepts is suitable for use as a broadband sound absorber design, and a transmission line model is presented that provides good comparison with their respective acoustic impedance spectra. This model can therefore be used to design acoustic liners to accurately achieve selected impedance spectra. Finally, the effects of increasing the perforated facesheet thickness are demonstrated, and the validity of prediction models based on lumped element and wave propagation approaches is investigated. The lumped element model compares favorably with measured results for liners with thin facesheets, but the wave propagation model provides good comparisons for a wide range of facesheet thicknesses.

Jones, Michael G.↗

The 27-28 October 1986 FIRE IFO cirrus case study - In situ observations of radiation and dynamic properties of a cirrus cloud layer

Observations are presented of cirrus cloud radiative, microphysical, and dynamic properties, their variability, and apparent scale sizes, as observed from NCAR Sabreliner on October 28, 1986. Broadband mass-absorption coefficients were deduced as a function of depth into the cirrus cloud and found to vary with particle dimension. Broadband volume absorption coefficients were deduced. By employing a diffusivity factor of 1.49 this agreement was maximized. Calculated infrared heating rates were typical of thin cirrus layers. The cloud top cooling and cloud base warming were observed to become more accentuated for the denser portions of cloud. The broadband emittances due to the cloud aerosol were found to approach 0.5 to 0.6. The cirrus clouds were observed to exhibit significant horizontal variability and a significant amount of scatter was evident when attempting to relate the broadband infrared and shortwave radiative properties. It is suggested that these radiative properties, which are modulated by the cloud elements, have their scales determined by the eddies detected in the analysis of wind components.

Smith, William L., Jr.↗

Highly Saturated Glassy Liquid Crystal Films Having Nano- and Microscale Thicknesses for High-Power Laser Applications

The optical properties of glassy liquid crystals (GLC’s) designed to provide high resistance to laser-induced damage are explored. GLC’s readily enable freezing of the anisotropic ordering of liquid crystals into the glassy state. This solidity avoids issues of fluid leakage while providing mechanical robustness and the promise of single-substrate coatings or stand-alone films of nanometer to micron thicknesses. A series of three increasingly saturated GLC’s was synthesized and tested for their thin-film (hundreds of nanometers to tens of micrometers) high-peak-power laser-damage resistance with nanosecond pulses at 1053 nm, 532 nm, and 351 nm, as well as their durability under continuous-wave, broadband ultraviolet illumination. As a result, the GLC’s with higher degrees of saturation demonstrated high resistance to laser-induced damage, extending from the near infrared to the ultraviolet spectral region.

36 MATERIALS SCIENCE↗

Comparison of the Forward and Reverse Photocycle Dynamics of Two Highly Similar Canonical Red/Green Cyanobacteriochromes Reveals Unexpected Differences

Cyanobacteriochromes (CBCRs) are cyanobacterial photoreceptors that exhibit photochromism between two states: a thermally stable dark-adapted state and a metastable light-adapted state with bound linear tetrapyrrole (bilin) chromophores possessing 15Z and 15E configurations, respectively. The photodynamics of canonical red/green CBCRs have been extensively studied; however, the time scales of their excited-state lifetimes and subsequent ground-state evolution rates widely differ and, at present, remain difficult to predict. Here, we compare the photodynamics of two closely related red/green CBCRs that have substantial sequence identity (~68%) and similar chromophore environments: AnPixJg2 from Anabaena sp. PCC 7120 and NpR6012g4 from Nostoc punctiforme. Using broadband transient absorption spectroscopy on the primary (125 fs to 7 ns) and secondary (7 ns to 10 ms) time scales together with global analysis modeling, our studies revealed that AnPixJg2 and NpR6012g4 have comparable quantum yields for initiating the forward ( 15Z P r → 15E P g ) and reverse ( 15E P g → 15Z P r ) reactions, which proceed through monotonic and nonmonotonic mechanisms, respectively. In addition to small discrepancies in the kinetics, the secondary reverse dynamics resolved unique features for each domain: intermediate shunts in NpR6012g4 and a Meta-Gf intermediate red-shifted from the 15Z P r photoproduct in AnPixJg2. Altogether, this study supports the conclusion that sequence similarity is a useful criterion for predicting pathways of the light-induced evolution and quantum yield of generating primary intermediate Φ p within subfamilies of CBCRs, but more studies are still needed to develop a comprehensive molecular level understanding of these processes.

59 BASIC BIOLOGICAL SCIENCES↗

Ligand-Structure-Dependent Coherent Vibrational Wavepacket Dynamics in Pyrazolate-Bridged Pt(II) Dimers

Bimetallic transition metal complexes have gained increasing attention because of their versatile functions in solar energy conversion and photonics applications arising from inter-metal electronic coupling. In bimetallic platinum (Pt) complexes, electronic communication between the Pt-centered and ligand-centered moieties have been shown to be critical for defining their excited-state dynamic trajectories undergoing either localized ligand centered (LC)/metal-to-ligand-charge-transfer (MLCT) transitions or delocalized metal-metal-to-ligand-charge-transfer (MMLCT) transitions. The branching of the excited-state intersystem crossing (ISC) trajectories are modulated through structural factors that alter the relative energies of the different states. In this study, we investigated the correlation of the structural factors influencing the excited state trajectories. Using femtosecond broadband transient absorption (fs-BBTA) spectroscopy, ultrafast dynamics in the excited state of two select Pt(II) dimers have been mapped out using their coherent vibrational wavepacket signatures in corresponding transient absorption spectra. To examine how the ligand moieties of the Pt(II) dimers influence excited-state dynamics and the coherent vibrational wavepacket behavior, here we carried out comparative studies on two pyrazolate-bridged Pt(II) dimers of the general formula [Pt( t Bu 2 Pz)(N^C)] 2 ( t Bu 2 Pz = 3,5-di-tert-butylpyrazole); N^C = 7,8-benzoquinoline (bzq, 1) or 1-phenylisoquinoline (piq, 2)). We found that photoexcitation into the low energy absorption bands of 1 and 2 respectively induce the formation of 1 MMLCT states from which ultrafast ISC proceeds, resulting in stimulated emission quenching and decoherence of the vibrational wavepacket motions. The results obtained in this study suggest that both energetics and the structural rigidity of the aromatic cyclometalating ligands in 1 and 2 can significantly influence dynamics along the excited state trajectory characterized by dephasing of the coherent oscillations. The collective results provide direct evidence of how ligand structure alters electronic dynamics along excited state trajectories associated with ISC processes, providing insight into using ligand design to steer photochemical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polariton Control of Molecular Charge Transfer in Perylene Diimide Semiconductors

We report the modulation of molecular charge transfer in a bay-substituted perylene diimide derivative embedded in a planar distributed Bragg reflector microcavity. Angle-resolved reflectance spectra confirm the formation of upper and lower polaritons with clear Rabi splitting, indicating strong coupling between the cavity mode and molecular excitons. Using broadband transient absorption spectroscopy, we compare the ultrafast dynamics of cavity and non-cavity films. While excited-state absorption and stimulated emission pathways remain largely unchanged, kinetic modeling reveals a moderate increase in the charge transfer rate and yield under strong coupling. This enhancement is attributed to a reduction in the effective driving force via the formation of the lower polariton, placing the system deeper into the Marcus inverted regime. Our results demonstrate a promising non-chemical method leveraging cavity quantum electrodynamics to modulate charge separation processes in molecular semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tracking carrier and exciton dynamics in mixed-cation lead mixed-halide perovskite thin films

Mixed-cation lead mixed-halide perovskites simultaneously possess structural stability and high power conversion efficiency. A thorough study of both carrier and exciton dynamics is needed to understand the photophysical properties that underpin its superior photovoltaic performance. By utilizing a broadband transient absorption spectroscopy, we observe the carrier and exciton dynamics in a FA 0.85 Cs 0.15 Pb(I 0.97 Br 0.03 ) 3 (FCPIB) perovskite by simultaneously resolving the carrier and exciton contribution to the transient change of the absorption spectra, from which the carrier density and exciton oscillator strength can be determined. Our data reveal a quick and significant conversion of the photogenerated carriers to excitons, on top of the usual carrier recombination process. Moreover, the decay of carrier density shows a change of kinetics from a second-order recombination at high pump fluence to a third-order recombination at low pump fluence. Our analysis utilizes band anharmonicity, presents an independent determination of electronic temperature and quasi-Fermi energy, and reveals an interesting interplay among the processes of carrier cooling, exciton formation/decay and carrier recombination, all as a function of time after photoexcitation. Our work demonstrates the use of pump fluence as a knob to tune the relative populations of carriers and excitons in halide perovskite materials.

36 MATERIALS SCIENCE↗

Jahn–Teller distortion controls electron transfer in photoexcited Cu( I ) donor–acceptor systems

The Jahn–Teller distortion (JTD) is a defining structural response to electronic excitation in Cu( I )-based transition metal complexes, yet its role in photoinduced electron transfer (PET) remains largely unexplored. Here, we demonstrate that the JTD governs charge separation (CS) through a vibronically controlled conical intersection in heteroleptic Cu( I ) bisphenanthroline–naphthalene diimide (CuHETPHEN-NDI) donor–acceptor dyads. Using 20-fs broadband transient absorption spectroscopy combined with coherent vibrational wavepacket (CVWP) analysis and quantum chemical calculations, we directly track nuclear motions that steer the system from the metal-to-ligand charge-transfer ( 1 MLCT) state to the CS state. Steric bulkiness of the pendant groups at the 2,9-positions of the phenanthroline ligand systematically slows both JTD and CS. Short-time Fourier transformation and Fourier filtering analyses identify two key vibrational signatures: a low-frequency breathing mode (∼100 cm −1 ) via a bond distance change between Cu and ligated Ns (Cu–N) that modulates the NDI anion absorption and acts as a vibronic coupling coordinate, and a higher-frequency mode (∼313 cm −1 ) that evolves along the PET trajectory. Normal mode analysis and potential energy surface calculations show that the JTD brings the 1 MLCT and CS states into degeneracy, while the Cu–N breathing motion dynamically modulates donor–acceptor electronic coupling to enable ultrafast nonadiabatic electron transfer. Steric hindrance exerted by the groups at the 2,9 positions of the phenanthroline ligands suppresses this vibronic coupling, leading to faster CVWP decoherence for the 313 cm −1 mode and slower CS. These findings unravel JTD-controlled vibronic coupling at conical intersection as a governing factor for CS and provide insight into designing Cu-based photosensitizers by harnessing structural dynamics to control PET.

Kim, Pyosang [Argonne National Laboratory (ANL), A↗

Breath analysis by ultra-sensitive broadband laser spectroscopy detects SARS-CoV-2 infection

Rapid testing is essential to fighting pandemics such as coronavirus disease 2019 (COVID-19), the disease caused by the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Exhaled human breath contains multiple volatile molecules providing powerful potential for non-invasive diagnosis of diverse medical conditions. We investigated breath detection of SARS-CoV-2 infection using cavity-enhanced direct frequency comb spectroscopy (CE-DFCS), a state-of-the-art laser spectroscopic technique capable of a real-time massive collection of broadband molecular absorption features at ro-vibrational quantum state resolution and at parts-per-trillion volume detection sensitivity. Using a total of 170 individual breath samples (83 positive and 87 negative with SARS-CoV-2 based on reverse transcription polymerase chain reaction tests), we report excellent discrimination capability for SARS-CoV-2 infection with an area under the receiver-operating-characteristics curve of 0.849(4). Our results support the development of CE-DFCS as an alternative, rapid, non-invasive test for COVID-19 and highlight its remarkable potential for optical diagnoses of diverse biological conditions and disease states.

60 APPLIED LIFE SCIENCES↗

Semiconductor-metal graded-index composite thin films for infrared applications

Theoretical/experimental studies have been carried out on germanium:silver (Ge:Ag) graded-index composite thin films which demonstrate that graded coatings, consisting of varied concentrations of Ag with respect to the Ge film thickness, exhibit different optical properties ranging from selective infrared (IR) reflectance to broadband IR absorptance. The graded coatings have been produced by dc magnetron cosputtering of Ge and Ag and the spectral properties are found to be stable against temperature. The coatings have been applied to an infrared tunnel sensor (micro-Golay cell) to improve the device performance.

Lamb, James L.↗

The Effect of Cumulus Cloud Field Anisotropy on Domain-Averaged Solar Fluxes and Atmospheric Heating Rates

Cumulus clouds can become tilted or elongated in the presence of wind shear. Nevertheless, most studies of the interaction of cumulus clouds and radiation have assumed these clouds to be isotropic. This paper describes an investigation of the effect of fair-weather cumulus cloud field anisotropy on domain-averaged solar fluxes and atmospheric heating rate profiles. A stochastic field generation algorithm was used to produce twenty three-dimensional liquid water content fields based on the statistical properties of cloud scenes from a large eddy simulation. Progressively greater degrees of x-z plane tilting and horizontal stretching were imposed on each of these scenes, so that an ensemble of scenes was produced for each level of distortion. The resulting scenes were used as input to a three-dimensional Monte Carlo radiative transfer model. Domain-average transmission, reflection, and absorption of broadband solar radiation were computed for each scene along with the average heating rate profile. Both tilt and horizontal stretching were found to significantly affect calculated fluxes, with the amount and sign of flux differences depending strongly on sun position relative to cloud distortion geometry. The mechanisms by which anisotropy interacts with solar fluxes were investigated by comparisons to independent pixel approximation and tilted independent pixel approximation computations for the same scenes. Cumulus anisotropy was found to most strongly impact solar radiative transfer by changing the effective cloud fraction, i.e., the cloud fraction when the field is projected on a surface perpendicular to the direction of the incident solar beam.

Hinkelman, Laura M.↗

Flap Side Edge Liners for Airframe Noise Reduction

One or more acoustic liners comprising internal chambers or passageways that absorb energy from a noise source on the aircraft are disclosed. The acoustic liners may be positioned at the ends of flaps of an aircraft wing to provide broadband noise absorption and/or dampen the noise producing unsteady flow features, and to reduce the amount of noise generated due to unsteady flow at the inboard and/or outboard end edges of a flap.

Jones, Michael G.↗

Semiconductor- Metal Graded Index Composite Thin Films for Infrared Applications

Theoretical/experimental studies have been carried out on Germanium:Silver (Ge:Ag) graded index composite thin films, which demonstrate that graded coatings, consisting of varied concentrations of Ag with respect to the Ge film thickness, exhibit different optica properties ranging from selective infrared (IR) reflectance to broadband IR absorptance.

Inhomogeneous↗

22” ADP Fan Rig Liners Design Report

A liner design study was conducted as part of a cooperative effort between five (5) government/industry teams that together seek to demonstrate the technology for designing and manufacturing acoustic liners that are twenty five percent (25%) more efficient than 1992 technology liners. The study emphasized teaming collaboration. The improved liners were designed by Pratt & Whitney and Boeing Airplane Company and built by Rohr Inc, and will be tested in the NASA/P& W 22-inch ADP fan rig at NASA Lewis Research Center's 9' x 15' wind tunnel. Design guidelines and decisions were made collectively during monthly design review telecons and at the formal final design review. The tools that were used to design the new improved liners were not new, but the process that was developed as part of this study that led into the evaluation and selection of the final and best liner designs is new. Until now, the liner design process as practiced by different industry teams varied greatly. Some procedures were based on empirical liner attenuation databases which could not adequately account for engine-to-engine hardwall fan noise spectral differences, while others were entirely theoretical. And regardless of which method one chose, the major difficulty was still the lack of understanding and knowledge of the actual hardwall fan source noise modal structure and farfield SPL spectra. The NASA-led effort to attempt actual measurements of the fan source noise modal structure by means of the rotating microphone array is expected to contribute significantly to the understanding of the nature of the fan tone noise modes, but the application to broadband noise is still a long way off. The new design process included consideration of the measured fan tone modes, but for the majority of the spectra a separate, systematic process was used. It is a common practice in the engine/nacelle industry that acoustic liners for new products are designed before actual measured hardwall engine far-field noise spectra are available. Target noise spectra are normally derived from existing engine noise databases with some adjustments to absolute SPLs and frequencies. This practice has been acceptable as long as the new engine was a derivative of the base engine. However, in the case of the ADP, the transition from a current engine base is too - great, and the adjustments could not adequately account for the quantum changes in SPL spectral differences. Examples were the 1992 single degree of freedom (SDOF) inlet and aft liners (designed by P&W) that would be used as the baseline liners against which the new improved liners' efficien¬cies would -be measured. As will be shown, these baseline liners have been found to be deeper than the desire optimum depths. The new liner design process begins with the selection of the target hard wall fan noise spectra. These spectra were obtained by scaling up (5.91 scale factor) the measured hardwall fan spectral data from the 22” ADP fan rig. Next, the modal energy contents for each 1/3-octave band center frequency of these hardwall fan noise spectra are estimated. (Within each 1/3-octave band center frequency, the model energy distribution approximation is for both tone and broadband noise). For the inlet noise, P&W uses a derivative of the NASA Lewis (Ed Rice's) method of classifying; and grouping propagating modes by their cutoff ratios. The next step is to assign energy level to each group of modes having the same cutoff ratio. In Ed Rice's model, the modes were grouped according to ten (10) cutoff ratio intervals with center values located at 1.026, 1.085, 1.155, 1.24, 1.35, 1.49, 1.69, 2.0, and 4.47 (with equal number of modes in each interval). The modes were assumed to have equal energy. P&W’s model expands the cutoff ratio-mode grouping into two hundred (200) smaller cutoff ratio intervals with center values located f1".'m 1.003 to 11.5 in 199 increasing incremental intervals. Next, P&W's model uses a "2-parameter" normal distribution as a template to assign energy levels to these 200 pre-determined cutoff ratio values (for each 1/3-octave band center frequency). In the past, P&W had conducted an extensive study to determine what "2-parameter" values are appropriate for fullscale inlet liners, and had developed a set of twenty-four (24) "2-pararneter" values (i.e. one for each 1/3-octave frequency band) that when used in Ed Rice's Inlet Attenuation Prediction Method produced predicted liner attenuations that closely matched measured liner attenuations from several P&W's engines. In the absence of actual measured tone and broadband modal data from the 22" ADP rig, the process will use P&W's proprietary set of "2-parameter" values for this liner design study. For the aft noise, Boeing uses a modal energy approximation that the "transport energy" of each propagating mode is equal. This approximation is almost the same as the equal energy per mode approximation, except for modes that are near cutoff. Boeing's model forces these modes to have lower energy levels. Both P&W and Boeing agreed that the "transport energy" approximation should work well for the ADP aft fan noise which appears to be dominated by broadband noise. The design process then proceeds to calculate the optimum liner impedances for each frequency in both the inlet and the aft. These optimum impedances represent the target impedances that the designed liners should have. Liners with impedances matching the optimum impedances at all frequencies are "ideal" liners. These ideal liners are theoretically the best liners. Unfortunately, it has been showed that it is impossible to design and build such ideal liners. The next best liners are ones that have impedances matching the optimum impedances over some frequency range (not all frequencies as for the ideal). This is accomplished by the use of "frequency weightings". Several of P&W's and Boeing's existing computer decks were used for optimizing and matching the designed liner impedances to the target optimum values (with the various frequency weightings specified). The optimization produces liner candidates with predicted liner impedances and descriptions of their physical liner characteristics. These candidate liner impedances are then used to predict their spectral attenuation characteristics which are then used together with the target hardwall fan noise spectra to determine the resulting treated noise spectra and PNLT values. Further optimization around the selected candidate designs yield final designs that are best in PNLT attenuations. Use of the optimization decks allowed a large number of liner candidates to be screened in a relatively short period of time. This design process is systematic and is efficient. The new inlet SDOF liner design obtained from the improved process was predicted to be 34% more effective (per unit area) than the 1992 baseline inlet liner. This inlet liner design is a 112 rayl wovenwiremesh facesheet over a 0.312-inch deep honeycomb core. The new aft SDOF liner design was predicted to be 52% more efficient than the aft baseline liner. The new aft SDOF liner is "segmented" with a shallower liner on the core cowl (inner duct wall) and a deeper liner on the fan cowl (outer duct wall). The shallower liner is a 70.6 rayl woven-wiremesh facesheet over a 0.141-inch deep honeycomb core. The deeper liner is a 68 rayl woven-wiremesh facesheet over a 0.309-inch deep honeycomb core. All liner dimensions are for the 22-inch model-scale ADP fan rig liners. The selected advanced liners are "segmented" double-layer (DDOF) liners for the inlet and aft locations. Also, for the inlet, a bulk liner with ceramic foam for wider broadband noise absorption was also selected. Triple-layer liner designs were not considered since the model scaled liners ( 1/5. 91) were dimensionally too small to be built correctly, and irrin earlier concept study, Boeing found a triple-layer to have only very small benefits over a double-layer. The inlet DDOF liner was predicted to be 83% more effective than the baseline. The inlet DDOF design is a 78 rayl facesheet over a 0.080 top cavity depth, a 68 rayl septum and a 0.227-inch bottom cavity depth. The inlet bulk liner is a 60 rayl facesheet over a 0.33-inch deep honeycomb filled with high temperature (HTP) ceramic foam with a density of 4.8 lb/cu.ft and a flow resistivity of 167 rayl/cm. The inlet bulk liner was predicted to be 83% more effective than the baseline liner. The aft DDOF liners are segmented with a shallower liner on the core cowl and a deeper liner on the fan cowl. The shallow DDOF liner is a 49.8 rayl facesheet over a 0.093-inch top cavity depth, a septum of 88.2 rayls over a 0.181-inch bottom cavity depth. The deep DDOF liner is a 12.9 rayl facesheet over a 0.140-inch top cavity depth, a septum of 53.1 ray ls over a 0.258-inch botom cavity depth. The segmented aft DDOF liners were predicted to be 86% more efficient than the baseline liner.

turbofan acoustic treatment↗

BELINDA: Broadband Emission Lidar with Narrowband Determination of Absorption. A new concept for measuring water vapor and temperature profiles

We present a new concept for differential absorption lidar measurements of water vapor and temperature profiles. The idea is to use one broadband emission laser and a narrowband filter system for separation of the 'online' and 'offline' return signals. It is shown that BELINDA offers improvements as to laser emission shape and stability requirements, background suppression, and last and most important a significant reduction of the influence of Rayleigh scattering. A suitably designed system based on this concept is presented, capable of measuring water vapor or temperature profiles throughout the planetary boundary layer.

Theopold, F. A.↗

Femtosecond Reflectance Spectroscopy for Energetic Material Diagnostics

Understanding the fundamental mechanisms underpinning shock initiation is critical to predicting energetic material (EM) safety and performance. Currently, the timescales and pathways by which shock-excited lattice modes transfer energy into specific chemical bonds remains an open question. Towards understanding these mechanisms, our group has previously measured the vibrational energy transfer (VET) pathways in several energetic thin films using broadband, femtosecond transient absorption spectroscopy. However, new technologies are needed to move beyond these thin film surrogates and measure broadband VET pathways in realistic EM morphologies. Herein, we describe a new broadband, femtosecond, attenuated total reflectance spectroscopy apparatus. Performance of the system is benchmarked against published data and the first VET results from a pressed EM pellet are presented. This technology enables fundamental studies of VET dynamics across sample configurations and environments (pressure, temperature, etc .) and supports the potential use of VET studies in the non-destructive surveillance of EM components.

42 ENGINEERING↗

Unusual Electrochemical Activity of Thin SiO 2 Layers Leads to Instability of Molecular Attachment in Hybrid Photoelectrodes

Hybrid photoelectrodes, comprised of a light-absorbing semiconductor and a surface-integrated molecular catalyst, are attractive for applications in artificial photosynthesis, since they combine the advantages of broadband semiconductor light absorption with the selectivity of molecular catalysis. A widely used class of hybrid photoelectrodes is based on Si substrates passivated by a thin (<3 nm) layer of silicon oxide, which is commonly prepared by controlled chemical or thermal oxidation, resulting in chemical oxide (ChO) or thermal oxide (ThO) layers, respectively. However, the electrochemical stability of these oxide layers, and the chemical stability of the semiconductor-molecule assembly in hybrid photoelectrodes, are not well understood, with evidence that covalently-bound molecules detach from the oxide surface upon application of cathodic bias. We have examined the intrinsic electrochemical reactivity of silicon oxide layers and how it affects the attachment of molecular monolayers. We determined that the surface of Si|ThO is primarily terminated with hydrophobic siloxane moieties, whereas that of Si|ChO contains a higher concentration of hydrophilic silanol groups. Initial high current densities for Si|ChO under applied bias up to -2 V vs. Ag/AgCl, decrease during repeated cyclic voltammetry scans, due to the consumption of surface-bound water. This is manifested by a reversible wave around -0.5 V in CH 3 CN solution, and a similar pH-dependent wave in water, revealing the pK a of the silanol groups to be ~4. Here, our combined observations support the electrochemically-induced dehydration of the SiO 2 surface, which converts silanol groups to siloxanes and proceeds through an H-atom intermediate that is most likely stabilized by pentavalent Si. We propose that similar reactivity is responsible for the electrochemical loss of alkylsiloxane-attached molecules under cathodic bias, which has important implications for the choice of catalyst attachment strategy in hybrid photoelectrodes.

14 SOLAR ENERGY↗