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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

High-Throughput In-Line Deposition of Silicon Oxide for Polycrystalline Silicon Passivating Contacts

Polycrystalline silicon passivating contacts rely on an ultrathin (1–2 nm) silicon oxide layer to minimize recombination at the wafer/oxide interface and regulate dopant diffusion. Traditionally formed by thermal or chemical oxidation, this oxide is herein replaced by silicon oxide deposited via aerosol impact-driven assembly (AIDA), enabling high wafer-per-hour throughput and precise thickness control. In this study, we show that AIDA coatings conformally cover planar or textured substrates and achieve a SiO x /poly-Si(n) structure with an implied open-circuit voltage (iV oc = 726 mV) and contact saturation current density (J 0 = 8.8 fA/cm 2 ). Furthermore, annealing AIDA SiO x films at elevated temperatures desorbs hydroxyl groups while the stoichiometry transitions toward SiO 2 , improving passivation quality. Together, these results highlight AIDA’s potential for scalable, high-throughput manufacturing of advanced passivating contacts, offering a cost-effective alternative to conventional low-pressure chemical vapor deposition and plasma-enhanced chemical vapor deposition-based silicon and oxide processes.

TOPcon↗
DOE OSTI2026

Coupled Roles of Surface Chemistry and Hydrogen-Assisted Cycling in Ruthenium Atomic Layer Deposition on Silicon Oxides

Ruthenium (Ru) is a promising interconnect material for advanced semiconductor technologies due to its favorable scaling characteristics, including a short electron mean free path and strong electromigration resistance. In semiconductor integration, silicon oxide-based dielectrics serve as dominant insulating materials and constitute ubiquitous interfaces for metallization; however, their formation-dependent surface chemistry and its impact on Ru growth remain insufficiently explored. Here, we investigate Ru ALD on native oxide SiO x (N-SiO x ) and thermally grown SiO 2 (T-SiO 2 ) as model substrates using bis(ethylcyclopentadienyl)ruthenium(II) [Ru(EtCp) 2 ] under two distinct reactant-sequence environments: AB-type (Ru(EtCp) 2 /O 2 ) and hydrogenassisted ABC-type (Ru(EtCp) 2 /O 2 /H 2 ). Under the AB-type process, both N-SiO x and T-SiO 2 exhibit pronounced nucleation delay. N-SiO x shows earlier nucleation and higher nucleation density than T-SiO 2 , plausibly attributed to differences in surface hydroxyl populations. Similar temperature-dependent phase evolution is observed on both substrates, with mixed Ru and RuO 2 phases at 250 °C and predominantly metallic Ru at 300 °C accompanied by increased morphological roughening. In contrast, incorporating an H 2 subpulse (ABC-type) mitigates nucleation delay, particularly on hydroxyl-deficient T-SiO 2 , thereby reducing the substratedependent disparity observed under AB cycling. Moreover, RuO 2 formation is suppressed even at 250 °C on both substrates, shifting growth toward more metallic Ru with reduced resistivity (∼20 μΩ·cm at ∼ 20 nm on N-SiO x ). These trends suggest that H 2 influences the surface reaction pathway, contributing to enhanced metallic stabilization and altered early stage growth kinetics. Overall, this work clarifies the coupled roles of substrate chemistry and reactant-sequence design in governing Ru nucleation and early stage film evolution, providing insight relevant to next-generation interconnect integration and future area-selective deposition strategies.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Proton Conducting Silicon Oxide Membranes as a Fluorine Free Alternative to Nafion for Low Temperature Water Electrolysis

Driven by environmental and health concerns related to per- and polyfluoroalkyl substances (PFAS), there has been growing interest in developing fluorine-free proton (H + ) exchange membrane (PEM) materials for fuel cells and water electrolyzers. In this study, we present a side-by-side comparison of the key transport properties of submicron thick, PFAS-free amorphous silicon dioxide (SiO 2 ) membranes to Nafion, a fluorinated polymer electrolyte membrane that represents the industry standard for PEM fuel cells and electrolyzers. Here, measurements of proton (H + ) conductivity (σ H + ), hydrogen (H 2 ) permeability (P H 2 ), and electrical resistivity (ρ e – ) were conducted using model thin films comprised of SiO 2 membranes deposited by atomic layer deposition (ALD). Although the H + conductivity of the SiO 2 membranes is 2–3 orders of magnitude lower than Nafion, the addition of phosphorus dopants (PO x ) improves H + conductivity such that the area specific membrane resistance of thin (<50 nm) PO x -doped SiO 2 membranes is more than an order of magnitude lower than Nafion-117. Importantly, the safe operation of such nanoscale membranes within a PEM electrolyzer is feasible thanks to the low H 2 permeability of dense SiO 2 -based membranes, which are predicted to limit H 2 crossover rates to acceptable levels for pressures up to ≈ 100 bar. As a proof-of-principle demonstration, a chip-scale water electrolyzer based on 100 nm thick PO x -SiO 2 membrane is shown to achieve a current density of 2 A cm –2 at a potential of 2.5 V. If this technology can be successfully scaled up, H + conducting oxide membranes offer an attractive PFAS-free alternative to Nafion for efficient and durable water electrolysis and fuel cell technologies.

Nafion↗
DOE OSTI2025

Electron Inversion and Tunneling at Silicon Thermal Oxide Interfaces for Solar-Driven Molecular Catalysis to Syngas

Semiconductor photoelectrodes are regularly coupled to solid-state heterogeneous catalysts to perform solar-driven reduction of CO 2 . Less frequently, molecular catalysts are employed to better control the reactivity toward desired products, yet the development of robust semiconductor/molecule interfaces has proven challenging. Here, we demonstrate that a 2–3 nm thermal oxide layer on Si exhibits stability in aqueous solution, high photovoltage, and a photocurrent density of ∼10 mA/cm 2 for the solar-driven photoelectrochemical reduction of a homogeneous molecular catalyst, producing syngas with an ∼2:1 H 2 to CO ratio. Because of a low defect density, the oxide interface forms an electron inversion layer with metal-like electron density at cathodic potentials. This inversion layer facilitates electron transfer to redox-active molecules via tunneling even if the molecule’s reduction potential is beyond the semiconductor’s conduction band edge. Using an electrolyte solution composed of a homogeneous cobalt bis(terpyridine) catalyst in a water/organic solvent mixture, stable photoelectrochemistry was observed under 1-sun illumination, exhibiting an ∼30% Faradaic efficiency for CO that was similar to a glassy carbon electrode under comparable conditions. Furthermore, the results demonstrate that an ultrathin thermal oxide interface is a robust platform for development of aqueous-stable, molecule-driven photoelectrocatalysis.

Catalysts↗
DOE OSTI2025

Photoelectrochemical Hydride Generation with Oxide-Coated Silicon

Photoelectrochemical generation of a potent organic hydride donor at silicon is demonstrated. Two different oxide-coated p-type silicon photoelectrodes reduced 1,2,3,5,6-pentamethyl-1H-benzo[d]imidazol-3-ium hexafluorophosphate, [PMBI][PF 6 ], to its corresponding imidazole hydride, PMBIH, in the presence of a proton source. Under 1 sun illumination, in acetonitrile with 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) buffer, the p-Si photoelectrodes convert PMBI + to PMBIH with good Faradaic efficiencies (FEs): 78% FE at −2.3 V vs Fc +/0 for Si|TiO 2 and 83% FE at −2.6 V vs Fc +/0 for Si|SiO 2 (where Si|SiO 2 represents silicon coated with an oxide layer). Generally, the Si|TiO 2 catalyzed the reaction at milder potentials than Si|SiO 2 , but the Si|SiO 2 had better selectivity for PMBIH generation over H 2 evolution than Si|TiO 2 . In light of prior studies of these photoelectrodes, the differences in selectivity and onset potential suggest a difference in mechanism, likely an outer-sphere electron transfer (ET) mechanism at the SiO 2 surface and potentially a proton-coupled ET process at the TiO 2 surface. To help understand reaction efficiency and identify areas of improvement, a thermochemical model for understanding net hydride transfer from the semiconductor to an acceptor in solution was developed. We find that the reactions in the present system are quite downhill. The high overpotentials (even while maintaining selectivity over H 2 evolution) emphasize the need for improved catalysts. Furthermore, this approach to evaluate the thermodynamics of net hydride transfer should be broadly valuable for electrochemical and photoelectrochemical processes.

14 SOLAR ENERGY↗
DOE OSTI2025

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↗
DOE OSTI2025

Photoelectrocatalytic reduction of CO 2 to formate using immobilized molecular manganese catalysts on oxidized porous silicon

The reduction of carbon dioxide (CO 2 ) to formate using molecular catalysts immobilized on high surface area porous silicon is described. Manganese complexes of the type ( R bpy)Mn(CO) 3 Br (bpy = 2,2′-bipyridine) were prepared with silatrane groups on the bpy ligand for attachment to oxide-coated porous silicon (SiO x -porSi). SiO x -porSi wafers were formed by heating hydrogen-terminated p-type porous silicon wafers under air, and the manganese complexes were immobilized on SiO x -porSi by heating at 80°C. The resulting hybrid photoelectrodes are photoelectrocatalysts for CO 2 reduction in acetonitrile containing 2.0 M triethylamine and 2.0 M isopropanol, yielding formate with high selectivity (>96%) and current density (∼0.6 mA/cm 2 ), excellent reproducibility, and a photovoltage of 280 mV at −1.75 V (versus ferrocenium/ferrocene) under 1 sun illumination. Here, the applied potential is close to the equilibrium potential for CO 2 reduction to formate. This work presents rare examples of immobilized molecular catalysts for CO 2 reduction to formate and the first on semiconducting silicon.

13 HYDRO ENERGY↗
DOE OSTI2025

Characterization of Performance Degradation Mechanisms in Low-Cost High Throughput DI-O3 Layer for Passivated Contact Silicon Solar Cells

Characterization and mitigating performance limiting defects in Silicon (Si) PV is one of key areas to be addressed to improve PV hardware costs and energy yield in order to lower the levelized cost of energy (LCOE) of installed PV cost to $0.02/kWh. As Si PV cells efficiencies have surpassed 22% and approaching 23%, the recombination at the metal contacts have become the focus point to be addressed. Passivated contact technologies—having a heterojunction with a band-gap larger than silicon between the metal and silicon—have emerged as a great potential for future highand ultrahigh-efficiency solar cells, as it concurrently reduces recombination and increases carrier selectivity, by incorporating thin films within the contact structure. Passivated contact Si solar cell technologies use a wide variety of tunnel layers—playing a crucial role to passivate metal contacts and tunnel charge carriers—including stoichiometric silicon oxide (SiO 2 ) grown by thermal oxidation and Low-Pressure Chemical Vapor Deposition (LPCVD) technique and silicon oxide (SiO x ) by hot nitric acid. However, thorough investigations on understanding the failure and performance degradation mechanisms associated with tunnel layers are still limited to date. Unlocking those degradation characteristics in crucial tunnel layers could improve the reliability and energy yield of passivated contact Si solar cells. Besides, the technique of growing aforementioned tunneling layers are low throughput, and requires high temperature processes and/or a vacuum environment. In this project, we investigated the performance degradation mechanisms of a low-cost high-throughput ozonated oxide (DI-O 3 ) tunnel layer for the passivated contact Si solar cells.

14 SOLAR ENERGY↗
DOE OSTI2024

Oxidation of Silicon Carbide with Atomic Oxygen through the Passive-to-Active Transition

The inelastic and reactive scattering dynamics of O( 3 P) atoms on a 6H-silicon carbide (SiC) surface were investigated as a function of temperature with a molecular beam-surface scattering technique that employed a rotatable mass spectrometer detector. One set of experiments used a pulsed hyperthermal beam that produced ~8 km s –1 O atoms, and another set of experiments used a continuous beam that contained O atoms with a nominal velocity of ~2 km s –1 . When exposed to the relatively low-flux, pulsed hyperthermal O-atom beam, a passive oxide layer on the SiC that formed at lower temperatures decomposed as the temperature increased above 1673 K. Instead of entering an active oxidation regime, a graphitic layer formed on the surface and largely protected the underlying SiC from incoming O atoms. Investigation of the oxide decomposition without O-atom bombardment revealed volatile Si and SiO products at the moment that the oxide decomposed, implying that Si sublimation occurs concurrently with oxide decomposition. In the experiment with the continuous (higher flux) O-atom beam, volatile SiO and CO products were observed after the passive oxide decomposed, indicating that active oxidation was reached. Finally, the results of this study provide evidence for the importance of Si sublimation within the active oxidation regime. Above the passive-to-active transition temperature, Si sublimation is an ongoing process, and continuous active oxidation will only occur if sufficient oxygen reacts with the surface to produce SiO more quickly than a graphitic layer can form. Thus, accurate models of SiC ablation by atomic oxygen must account for multiple competing mechanisms that depend on the surface temperature and incident O-atom flux.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Effect of 316 stainless steel powder processing conditions on microstructure

One parameter that has both economic and performance effects in the manufacturing of steel parts is the powder feedstock used. 316 L steel powder can be produced through water atomization or gas atomization, where both the powder size and the atomization process determine the cost of powder feedstock. Gas atomized powder is spherical and has a lower oxygen content than water atomized powder, making it the preferred choice for performance, but comes at a higher financial cost. Here, in this study, various 316 L powder batches are characterized to understand physical properties and microstructural variations. Density and flowability were determined using gas pycnometry and Hall flow tests. Powder morphology and porosity were qualitatively analyzed via optical microscopy and scanning electron microscopy, Finally, transmission electron microscopy was used to determine changes in phases present. Spherical gas atomized powder of 30–100 μm contained Mn$-$Si rich oxides both on the surface and within the matrix. Meanwhile, irregular water atomized powder 30 μm in diameter contained silicon oxides without manganese. All powder particles contained a nickel rich cellular structure which was shown to support the formation of additional phases. While literature has observed general microstructural features across 316 L powder particles, transmission electron microscopy (TEM) in this study has identified variations in precipitation and cell structures. Information regarding morphology, flowability, density, and phase distributions can be applied to understand variations in part consolidation, which will in turn show which powder aspects are significant for production.

Chemical segregation↗
DOE OSTI2025

In Situ Characterization of Surface Recombination in p-Si/SiO x Based Photoelectrochemical Cells

Time-resolved infrared (TRIR) and electrochemical impedance spectroscopy (EIS) were utilized to quantify surface states present at silicon oxide (SiO x ) protected crystalline p-Si electrolyte interfaces. The primary goal was to identify p-Si/SiO x photoelectrodes with both low surface recombination rates and efficient multi-electron transfer to an acceptor present in the external electrolyte. Three SiO x layers were investigated: native oxide (nOx), chemical oxide (cOx), and rapid thermal annealed (RTA) thermal oxide (tOx). Comparative study with [Ru(bpy) 3 ](PF 6 ) 2 as the electron acceptor indicated that tOx was most optimal with a small effective recombination rate, multi-electron transfer capability, and photovoltage of 500 ± 50 mV. A secondary goal was to analyze the surface recombination rates with the Shockley–Read–Hall (SRH) kinetic model. Two surface states were identified from this analysis, one closer to the CB edge (V t,1 ) and the other near the midgap (V t,2 ). EIS and SRH analyses revealed that a forming gas (5% H 2 /N 2 ) anneal (FGA) decreased surface recombination for tOx and nOx through a lower density of surface states. In the case of tOx, the infrared data indicated that V t,2 was completely removed. Here, the energetic positions of the band edges were correlated with the surface state density; low densities corresponded to more favorable potentials for inversion layer formation, which is expected to be most optimal for photocatalysis. Collectively this study indicates that the free carrier dynamics provided by TRIR represent a powerful in situ probe of the band edge and the surface state energetics in silicon based photoelectrochemical cells.

Electrochemical Impedance Spectroscopy↗
DOE OSTI2025

Sandwiching of MOF nanoparticles between graphene oxide nanosheets among ice grains

Current strategies to tailor the formation of nanoparticle clusters require specificity and directionality built into the surface functionalization of the nanoparticles by involved chemistries that can alter their properties. Here, we describe a non-disruptive approach to place nanomaterials of different shapes between nanosheets, i.e., nano-sandwiches, absent any pre-modification of the components. We demonstrate this with metal-organic frameworks (MOFs) and silicon oxide (SiO 2 ) nanoparticles sandwiched between graphene oxide (GO) nanosheets, MOF-GO and SiO 2 -GO, respectively. For the MOF-GO, the MOF shows significantly enhanced conductivity and retains its original crystallinity, even after one-year exposure to aqueous acid/base solutions, where the GO effectively encapsulates the MOF, shielding it from polar molecules and ions. The MOF-GOs are shown to effectively capture CO 2 from a high-humidity flue gas while fully maintaining their crystallinities and porosities. Similar behavior is found for other MOFs, including water-sensitive HKUST-1 and MOF-5, promoting the use of MOFs in practical applications. The nanoparticle sandwich strategy provides opportunities for materials science in the design of nanoparticle clusters consisting of different materials and shapes with predetermined spatial arrangements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Nanoscopic Plugs Block Hydrogen Crossover in Submicron Thick Proton-Conducting SiO 2 Membranes for Water Electrolysis

Zero-gap electrolyzers based on submicron thick proton-conducting oxide membranes (POMs) represent a promising approach to increasing the efficiency of H 2 production from water electrolysis while moving away from conventional perfluorosulfonic acid (PFSA) membranes. A critical barrier to the commercialization of such electrolyzers is that the ultrathin nature of POMs, which is necessary to achieve low cell resistance, makes them more susceptible to defects that can lead to unacceptably high rates of H 2 crossover. Herein, we demonstrate an approach to mitigate this problem through selective deposition of carbon-containing silicon oxide (SiO x C y ) “nanoplugs” into the defects of submicron thick SiO 2 membranes using a facile electrochemically mediated deposition process. Selective deposition of nanoplugs within the defects was verified by multiple characterization techniques, while scanning electrochemical microscopy (SECM) was used to confirm selective plugging of H 2 -crossover hotspots associated with defects at identical locations. Thanks to the use of nanoplugs, the H 2 permeance of 250 nm thick SiO 2 membranes was reduced by 5 to 6 orders of magnitude compared to the unmodified atomic layer deposition (ALD) SiO 2 membranes while having negligible impact on the ionic resistance of the membrane. These plug-modified membranes also enabled safe and stable operation of a zero-gap full cell electrolysis cell, in contrast to cells lacking nanoplugs that produced anode effluent streams having H 2 concentrations near or exceeding the lower flammability limit (LFL) of H 2 . Furthermore, beyond water electrolysis, this defect-sealing strategy has the potential to be broadly implemented in other applications, such as fuel cells and flow batteries, offering a versatile solution to mitigate crossover-related performance losses.

ALD SiO2↗
DOE OSTI2024

The Critical Influence of Spin–Dry Technique on the Surface Passivation Quality of Crystalline Silicon Solar Cell Structures

This study examines the effects of spin-dry (SD) and N 2 blow-dry (ND) techniques on the quality and surface passivation performance of silicon oxide grown in ozone-dissolved deionized water. The SD method achieves greater oxide thickness uniformity, averaging 1.39 nm ± 4.17% across 49 points, compared to 1.68 nm ± 21.67% for the ND wafers. However, persistently poor passivation of ozonated oxide-grown wafers following the SD process is exhibited, with carrier lifetime, τ eff < 0.3 ms and saturation current density, J 0 (per side) ranging from 26 to 45 fA cm 2 . These findings are analyzed in the context of the fundamental phenomena involved in the drying processes of both techniques. Following this, an optimized spin-drying process is developed, resulting in improved τ eff and J 0 values of 1.4 ms and 5.6 fA cm –2 , respectively. Scanning electron microscopy further confirms that the oxide films dried with the enhanced SD technique are free of pinholes.

14 SOLAR ENERGY↗
DOE OSTI2025

Molecular Imaging of Microbially Induced Corrosion of Synthetic Archeological Glasses by a Rhizosphere Bacterium

Microbially induced corrosion (MIC) focuses on the degradation of solid materials, such as glass or metal. Soil microbes are often associated with the corrosion of foreign objects in the rhizosphere. Paenibacillus polymyxa SCE2, a facultative anaerobic bacterium in soil, is of the same genus as bacteria found near nuclear waste disposal sites. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used for imaging surface changes induced by P. polymyxa SCE2 cultured on two synthetic glass coupons to represent natural analogs of materials that were studied in relation to the vitrification of nuclear waste. Multimodal imaging was used to verify bacterial coverage across the glass surface after long-term growth. ToF-SIMS spectral analysis showed detection of glass component ions, such as silicon oxide (m/z – 59.96 SiO 2 – ) and aluminum oxide (m/z – 101.95 Al 2 O 3 – ), and biofilm’s extracellular polymeric substance (EPS) components, such as pentadecanoic acid (m/z – 241.22 C 15 H 29 O 2 – ) and sterol lipids (m/z – 311.16 C 20 H 23 O 3 – ). ToF-SIMS spectral, imaging, and depth profiling analyses showed that the glass rich in silica and other light elements (“granite glass”) had more “corrosion related” peaks than the glass that was less silica-rich and contained more iron (“dike glass”). Furthermore, these surface and interface compositional and spatial differences observed in the mass spectra and imaging were attributed to bacterial metabolism and an electron transfer mechanism influenced by morphological and compositional differences between the two types of glasses. ToF-SIMS is effective in studying microbial effects, bringing new molecular insights into MIC in a broader context of materials degradation.

Amorphous materials↗
DOE OSTI2025

Optically Addressable Light Valve Based on a GaN:Mn Photoconductor

Semi-insulating manganese-doped gallium nitride (GaN:Mn) layers epitaxially grown on unintentionally doped GaN substrates were used as photoconductors in optically addressable light valves (OALVs) to withstand higher operational laser fluences compared to current state-of-the-art OALVs where bismuth silicon oxide (BSO; Bi 12 SiO 20 ) layers are used as photoconductors. GaN:Mn promises to be an exciting material for optoelectronic operations due to its large laser fluence handling capability and photoresponsivity near the band edge. The laser damage thresholds for the semi-insulating epitaxial GaN:Mn layer and the n-type substrate layer were measured to be 2.4 and 4.2 J/cm 2 , respectively. These are 6–10 times higher than that of BSO (0.4 J/cm 2 ). These measurements were performed by exposing ~200 sites on the samples to increasing fluence levels from a Gaussian pulsed Nd:YAG laser system (1064 nm) operating at a 5 Hz repetition rate with a 3 ns pulse width. Photoresponsivity of the GaN:Mn material was investigated at discrete wavelengths of 447, 405, and 380 nm. Further, the peak photoresponsivity was observed under an illumination wavelength of 380 nm and is attributed to stronger absorption. The OALV was fabricated by attaching a 110-μm-thick GaN:Mn layer grown on a 280-μm-thick n-GaN layer to a 3-mm-thick BK7 optical window. A twisted nematic E7 liquid crystal was introduced to the 5 μm gap between the two components. Transmission levels of >90% were achieved for the fabricated OALVs for a peak voltage of 40 V, constrained by transmission “bleed-through”.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Syngas Production at Si Hybrid Photoelectrodes Modified with Re(I) and Mn(I) Tricarbonyl Phenanthroline Complexes Containing Reactive Aryl Azide Groups

We installed molecular CO 2 reduction (CO 2 R) catalysts directly onto Si (photo)electrodes. The highly reactive M(5-azido-1,10-phenanthroline)(CO) 3 X (where M = Mn or Re, X = Br or Cl) complexes readily bubbled when dissolved in polar organic solvents, in both the presence and absence of an ultraviolet light source. When placed on hydrogen-terminated Si (H-Si) and native silicon oxide (SiOx), similar amounts of the complex were attached to the surface under illumination (367 nm, 50–200 mW/cm 2 ) or in the dark. Surprisingly, these films revealed submonolayer coverages instead of the multilayered structures we expected. DFT analyses support monolayer formation, showing that the triplet-state nitrene of the complex is more energetically favorable than the singlet state. Using controlled-potential electrolysis experiments, we showed that Re- and Mn-containing films on pSi photoelectrodes generated small amounts of CO when exposed to 1 atm of CO 2 and 1 sun illumination. These amounts of CO were an order of magnitude greater than control surfaces, producing 5.59 × 10 –7 mol CO/h for Re(az-phen) and 7.83 × 10 –7 mol CO/h for Mn(az-phen) films. Much of the charge passed at the pSi electrodes was consumed by the competing hydrogen evolution reaction, which we attribute to the low molecular coverage and the presence of native oxide on the electrode surface after attachment. Finally, this work demonstrates the feasibility of reacting azide-containing ligands with Si surfaces. Still, it highlights the need for alternative ligand structures and reaction conditions to form multilayer films.

azides↗
DOE OSTI2025

Layer-by-layer growth of graphene oxide multilayers using robust interlayer linking chemistry. 1. Zr-bisphosphates

Graphene oxide (GO) holds substantial interest because of its utility in applications ranging from chemical sensing to catalysis and energy storage. We report on the layer-by-layer formation of graphene oxide phosphate (P-GO) multilayers on silica and oxidized silicon supports, with the layers connected via Zr-bisphosphate (ZP) linking chemistry. Layers were grown either directly by ZP linkages between P-GO sheets, or with the use of 1,4-phenylene bisphosphate (BP1) or [1,1′-biphenyl]4,4′-diyl bisphosphate (BP2). The layers have been characterized using optical null ellipsometry, X-ray photoelectron spectroscopy (XPS), UV-visible absorption spectroscopy and scanning electron microscopy (SEM). There is a linear dependence of assembly thickness on the number of layers deposited and the integrated area of the optical absorbance bands also increases linearly with number of layers deposited. XPS data provides information on interlayer linking stoichiometry. SEM images provide insight into the morphology of the adlayers, suggesting the structure and length of the interlayer linking moieties used in the multilayer assembly play a significant role in the organization of the resulting system.

Mukherjee, Neelanjana [Michigan State University, ↗