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At least 199 records · Page 11

Bio-inspired Surface Structures to Mitigate Interfacial Particle Adhesion and Erosion - A Review

Lunar dust known as regolith is a huge challenge for lunar exploration missions. Formed over millennia by a complex process involving impacts of meteoroids and micrometeoroids on the lunar surface, lunar dust is porous, highly abrasive with sharp jagged edges, chemically reactive, electrostatically charged and sometimes magnetic. The chemical composition and thickness of the dust layer also varies in different regions of the lunar surface. From samples obtained by previous lunar missions, the average particle size is below 100 microns. This dust has the tendency to strongly adhere to any exposed surfaces, and often degrades the material functionality to eventually cause failure. Any material on the lunar surface is also subject to harsh temperature cycles ranging from -178 ̊C to + 123 ̊C and extreme ultraviolet radiation. While on the lunar surface, different classes of materials would be required for different applications. Advanced materials have been and will be used throughout the lunar lander, habitat, and mission equipment. Examples include: polymeric materials for astronaut protective clothing; metals and ceramics for the lunar lander legs and habitats, and excavating equipment; and semiconductors for solar panels and on-board electronics. In all these applications, the surfaces of the materials are expected or understood to be exposed to the extreme lunar environment condition that includes the regolith dust. During the Apollo missions, the dust clung to and abraded the astronaut’s suits, degraded seals, optics, clogged sensors and reduced performance of thermal radiators. The lunar dust adheres to the surface by various mechanisms, which include electrostatic and Coulombic interactions, Van-der-Waals forces, magnetic forces, mechanical interlocking, chemical bonding and donor-acceptor interactions. There are three primary strategies for developing technologies to minimize the lunar dust adhesion: active, passive and a combination of active and passive. In the active approach, an external energy is needed to prevent or remove particles from collecting on the surface. Mechanically powered brushes and electrodynamic dust screens are two examples. In the passive approach, no external power is needed, and the material surface properties are able to mitigate dust adhesion. A well-known example of this strategy is the low work function coatings for non-stick surfaces. In most cases a combination of active and passive methods might be needed to optimally manage the lunar regolith. The passive method is significantly more attractive as it does not require any external power or an additional control subsystem. These approaches optimize the mission payload and reduce risk. Surface modification to minimize the dust adhesion is thus very important to lunar missions. Here, naturally evolved surface structures might provide guidance for solutions. There are several factors that have to be considered for minimizing particle adhesion to a surface. These include the substrate material properties, surface topography, chemistry, and the characteristics of the adhering particles. When engineering a surface, the substrate material chosen would be dependent on the needs of the application. Tailoring the surface microstructure or chemistry opens up more possibilities for its optimal utilization

Lunar Dust↗

Advances in Carbon Electrode Integration for Stable and Efficient Perovskite Solar Cells and Modules

Carbon-electrode-based perovskite solar cells (C-PSCs) have emerged as a cost-effective and scalable alternative to noble-metal-based PSCs, addressing critical challenges related to device stability, fabrication complexity, and commercialization potential. This review explores the recent progress in C-PSC development, focusing on the benefits of carbon electrodes (CEs), including their hydrophobicity, chemical inertness to halide corrosion, and compatibility with low-temperature cost-effective solution-based deposition methods. Despite relatively lower power conversion efficiencies (PCEs) than their metal (e.g., Au/Ag) counterparts, recent advances in carbon paste formulation, interfacial contact engineering, and work function modification have elevated C-PSC efficiencies above 22%. This review further examines strategies to enhance electrode conductivity, interfacial properties, and charge selectivity to further increase C-PSC performance. Progress in carbon-electrode-based perovskite solar modules (C-PSMs), particularly within mesoporous and planar architectures, is also analyzed, revealing significant developments in active area scaling and long-term stability. Notably, the limited research in inverted (PIN) C-PSCs is also highlighted as a compelling opportunity for innovation, given the architecture's inherent advantages in flexibility, tandem integration, and low-temperature processing. Collectively, these insights affirm the potential of C-PSCs and C-PSMs to deliver affordable, stable, and high-performance photovoltaics suitable for scalable deployment.

Carbon Electrodes↗

Co‐Doping Approach for Enhanced Electron Extraction to TiO 2 for Stable Inorganic Perovskite Solar Cells

Inorganic perovskite CsPbI 3 solar cells hold great potential for improving the operational stability of perovskite photovoltaics. However, electron extraction is limited by the low conductivity of TiO 2 , representing a bottleneck for achieving stable performance. In this study, a co‐doping strategy for TiO 2 using Nb(V) and Sn(IV), which reduces the material's work function by 80 meV compared to Nb(V) mono‐doped TiO 2 , is introduced. To gain fundamental understanding of the processes at the interfaces between the perovskite and charge‐selective layer, transient surface photovoltage measurements are applied, revealing the beneficial effect of the energetic and structural modification on electron extraction across the CsPbI 3 /TiO 2 interface. Using 2D drift‐diffusion simulations, it is found that co‐doping reduces the interface hole recombination velocity by two orders of magnitude, increasing the concentration of extracted electrons by 20%. When integrated into n–i–p solar cells, co‐doped TiO 2 enhances the projected T S80 lifetimes under continuous AM1.5G illumination by a factor of 25 compared to mono‐doped TiO 2 . This study provides fundamental insights into interfacial charge extraction and its correlation with operational stability of perovskite solar cells, offering potential applications for other charge‐selective contacts.

14 SOLAR ENERGY↗

Breaking the passivation barrier via d-p orbital optimization for stable hydrogen production and sulfion upgrading

The development of energy-efficient hydrogen production technologies represents a critical pathway toward achieving global carbon neutrality objectives. This work provides fundamental insights into overcoming catalyst passivation challenges in sulfide oxidation reaction (SOR)-coupled hydrogen evolution reaction (HER) systems through precise orbital hybridization engineering. Our theoretical simulations reveal that sulfur-passivated ruthenium surfaces can effectively modulate d-p orbital hybridization, significantly reduce d-electron activity while stabilizing long-chain S 8 species and decreasing intermediate adsorption energies. Furthermore, metal carbides/ruthenium heterostructure (MC/Ru, M = V, Mo, W) was designed to achieve simultaneous optimization of both HER (∆G H* = −0.11 eV) and SOR (∆G RDS = 1.51 eV) via work-function-mediated interfacial electron transfer, which effectively tailors surface electronic states. Guided by theoretical predictions, we successfully synthesized a series of metal carbides/ruthenium/nitrogen-doped carbon catalysts based on a solid-phase reaction and designated as MC/Ru@NC (M = V, Mo, W). The optimized VC/Ru@NC catalyst exhibits exceptional performance in a membrane-free two-electrode system, achieving an ultralow cell voltage of 0.76 V at 200 mA cm −2 with outstanding stability over 1600 h, while maintaining 97.5 % Faradaic efficiency for hydrogen production and 73.8 % sulfur recovery efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Suppressed deprotonation enables a durable buried interface in tin-lead perovskite for all-perovskite tandem solar cells

Low-band-gap tin (Sn)-lead (Pb) perovskites are a critical component in all-perovskite tandem solar cells (APTSCs). Current state-of-the-art Sn-Pb perovskite devices exclusively use poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) as the hole-transport layer (HTL) but suffer from undesired buried-interface degradation. Here, we show that the deprotonation of the –SO 3 H group in PSS is the root cause of the interface degradation due to its low acid dissociation constant (pK a ), leading to acidic erosion and iodine volatilization in Sn-Pb perovskites. We identify that HTL featuring the carboxyl (–COOH) group with a higher pK a , such as poly[3-(4-carboxybutyl)thiophene-2,5-diyl] (P3CT), can suppress deprotonation and strengthen the interface, mitigating the buried-interface degradation. Motivated by established P3CT modification, we introduce Pb doping to P3CT to increase its work function and reduce interfacial energy loss. Furthermore, we fabricate APTSCs with a champion efficiency of 27.8% and an operational lifetime of over 1,000 h, with 97% retaining efficiency under maximum power point tracking.

08 HYDROGEN↗

Enhancing microsegregation during rapid directional solidification through ternary microalloying

The nano-cellular dendritic microstructure formed during rapid directional solidification in powder bed fusion additive manufacturing creates unique properties such as simultaneous improvement in strength and ductility. However, process control of microsegregation features remains challenging due to low sensitivity of critical solidification mechanisms to process parameters. This study leverages microalloying to achieve large changes in dendrite composition, microstructure, and interdendritic zone width during laser powder bed fusion without modifying process parameters. CALPHAD simulations predict that the addition of Zr significantly steepens the solidus line of the dilute Cu-Cr alloy system, leading to enhanced Cr rejection into the melt and greater than 95% reduction in solubility of Cr in the solidified Cu matrix. Experimental validation using time-of-flight secondary ion mass spectrometry and Kelvin probe force microscopy reveals that the ternary alloy containing 0.01 wt% Zr exhibited wider interdendritic regions compared to the binary, a significantly higher number of Cr-rich particles within interdendritic regions, near-complete ejection of oxygen impurities from the matrix, and greater nanoscale work function contrast. These features indicate more aggressive Cr segregation in the presence of Zr and a purer Cu matrix and provide a potentially robust method for engineering the nano-cellular dendritic solidification microstructure.

CALPHAD↗

Construction of MoS 2 /NiS 2 heterostructure with fast interfacial reaction kinetics for ultrafast sodium storage

Constructing heterostructure is a valid method to reinforcing sodium storage performance of transition metal chalcogenides materials. Herein, a simple, safe and controllable one step hydrothermal method is proposed to synthesize MoS 2 /NiS 2 heterostructure. Due to the difference in band gaps and work functions of MoS 2 and NiS 2 , the charges are redistributed at the MoS 2 /NiS 2 heterointerfaces, thereby accelerating the migration of electrons and Na + . The heterointerfaces provide extra active sites for storing Na + , thus increasing the sodium storage capacity of the heterostructure. Furthermore, the distinct redox potentials of NiS 2 and MoS 2 promote the structural stability of MoS 2 /NiS 2 heterostructure during the electrochemical reaction processes. Consequently, the obtained MoS 2 /NiS 2 heterostructure exhibits superior rate properties (339.4 mAh g –1 at 10 A g –1 ) and ultra-stable cycling stability (480.5 mAh g –1 after 350 cycles at 1 A g –1 ). Finally, this paper presents a valid strategy for creating heterostructure anodes with excellent sodium storage properties.

25 ENERGY STORAGE↗

Adsorption, charge transfer and a coverage-driven transition of alkali metals on rutile TiO 2 (110)

The interaction of alkali metals with metal oxide surfaces is central to tuning surface reactivity in heterogeneous catalysis and photocatalysis. Here we present a comprehensive DFT+U study of the adsorption of alkali metals (Li, Na, K, Rb, Cs) on the (110) surface of rutile TiO 2 . At low coverage (θ = 1/8), all alkali metals bind preferentially to bridging oxygen sites with adsorption energies in the range −4.06 to −3.33 eV, transferring nearly one full electron (0.92–0.99 |e|) to the substrate and inducing Ti 4+ → Ti 3+ reduction. The excess charge localizes preferentially at subsurface Ti sites in the form of small polarons. Diffusion barriers indicate facile motion along bridging-oxygen rows, whereas inter-row hopping is strongly hindered. Coverage effects were examined systematically for potassium: adsorption energy and charge transfer per K atom decrease monotonically with increasing θ. Strikingly, a sharp energy discontinuity occurs between θ = 4/8 and θ = 5/8 (ΔE ≈ 1 eV per atom), which we identify as a coverage-driven structural transition arising from steric packing constraints and enhanced K–K electrostatic repulsion once every (1×1) surface cell is occupied. This structural transition perfectly correlates with a dramatic drop in the work function down to an ultra-low minimum of 0.84 eV at θ=5/8, followed by a metallization- driven recovery at higher coverages. Ab initio molecular dynamics simulations confirm zigzag K arrangements at moderate coverage (θ = 1/3), while at high coverage (θ = 2/3) short-range K–K correlations emerge without long-range order. These results provide atomistic insight into the structure–activity relationships underlying alkali promotion effects on oxide-supported catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating Cu-Site Doped Cu–Sb–S Nanoparticles Using Photoelectron and Electron Paramagnetic Resonance Spectroscopy

Tetrahedrite (Cu 12 Sb 4 S 13 ) and famatinite (Cu 3 SbS 4 ) are good candidates for green energy applications because they possess promising thermoelectric and photovoltaic properties as well as contain earth-abundant and nontoxic constituents. Herein, X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and electron paramagnetic resonance spectroscopy (EPR) methods examined inherent electronic properties and interatomic magnetic interactions of Cu-site doped tetrahedrite and famatinite nanomaterials. An energy-efficient modified polyol method was utilized for the synthesis of tetrahedrite and famatinite nanoparticles doped on the Cu-site with Zn, Fe, Ni, Mn, and Co. This is the first parallel study of tetrahedrite and famatinite nanomaterials with XPS, UPS, and EPR methods alongside a systematic analysis of dopant-dependent effects on the electronic structure and magnetic interactions for each material. XPS showed that the Cu and Sb species in tetrahedrite and famatinite possess different oxidation states, while UPS characterization reveals larger dopant-dependent shifts in the work function for tetrahedrite nanoparticles (4.21 to 4.79 eV) than for famatinite nanoparticles (4.57 to 4.77 eV). Finally, all famatinite nanoparticles display an EPR signal, indicating trace amounts of paramagnetic Cu(II) present below the detection limit of XPS. For tetrahedrite, EPR signatures were observed only for the Zn-doped and Mn-doped nanoparticles, suggesting signal broadening from Cu–Cu spin exchange or spin–lattice relaxation. This study demonstrates the complementary nature of XPS and EPR techniques for studying the oxidation states of metals in solid-state nanomaterials. Comparing the electronic and magnetic properties of tetrahedrite and famatinite while studying the impact of dopant incorporation will guide future endeavors in designing sustainable, high-performance materials for renewable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fundamental Interactions of Bimetallic Cu x Pd y ( x + y = 4) Clusters Supported on the α-WC(0001) Surface and Their Performance for CO 2 Adsorption and Dissociation

The tungsten carbide α-WC(0001) surface, an active system for the activation of H 2 and important hydrogenation processes involving unsaturated hydrocarbons, can serve as a support of bimetallic clusters to produce materials with unique catalytic properties, opening routes for a wide range of technical applications. In particular, Cu x Pd y clusters are of particular interest because they combine metals with different properties. A stochastic method was applied to obtain the geometry of Cu x Pd y (x + y = 4) bare clusters, evaluating thousands of possibilities to obtain stable structures, yielding one isomer for Cu 4 , Cu 2 Pd 2 , Cu 1 Pd 3 , and Pd 4 and two isomers for Cu 3 Pd 1 . These clusters were supported on C and W terminations of the tungsten carbide (0001) surface, exploring all of the binding possibilities. The adsorption energies on the C and W terminations are in the ranges from −2.51 to −3.02 eV and from −2.26 to −3.30 eV, respectively. The strongest and weakest binding was seen for monometallic Cu 4 and Pd 4 clusters on both C and W terminations, while the Cu-Pd bimetallics have intermediate adsorption energies but lack a clear trend in terms of composition. The location of Cu x Pd y clusters over the (0001) surface induces a decrease in the work function relative to the pristine surface, while the cluster-surface Bader charge transfer and variations in the partial density of states point to changes in the electronic structure of the carbide atoms upon binding of the metallic clusters. The d-band center of the Cu x Pd y deposited on WC(0001) indicates an intermediate reactivity among Cu(111) and Pd(111) surfaces, modulating the reactivity with small numbers of Cu and Pd atoms, i.e., atom economy in catalyst design. The likelihood of existence of the most stable Cu x Pd y (x + y = 4) clusters in the temperature range of 298-400 K is 100%. The composite Cu x Pd y /α-WC(0001) (x + y = 4), is a nontrivial system since 22 isomers are needed to completely describe its structural properties. Among the isomers, seven structures are necessary to represent Cu 3 Pd 1 /α-WC(0001), five for Pd 4 /α-WC(0001), two for Cu 4 /α-WC(0001), and four for Cu 2 Pd 2 /α-WC(0001) and Cu 1 Pd 3 /α-WC(0001). The large number of cluster isomers supported on the tungsten carbide surface opens the door for several applications in the heterogeneous catalysis of the Cu x Pd y /α-WC(0001) composite, with the possibility of modulating the geometric, electronic, and chemical properties according to a desired application. Test studies for the adsorption of CO 2 indicate that the Cu x Pd y /α-WC(0001) composites are highly active for the adsorption and decomposition of the molecule, with bimetallic and admetal-carbide interactions playing a key role in the binding performance. In conclusion, this high activity indicates that these systems should be useful as catalysts for the conversion of CO 2 to oxygenates or light alkanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial Charge Transfer and Substrate-Dependent Oxidation States Drive SMSI Enhancements in Cobalt Oxide Films

Here, we investigated the mechanisms underlying strong metal-support interactions in CO oxidation using model systems where noble metal crystals support reducible, monolayer-thick CoO x films. The effect of the Co oxidation state, film thickness, and substrate identity were studied in varying reaction conditions using ambient pressure X-ray photoelectron spectroscopy. At low O 2 pressures, the same oxide phase forms on both Pt(111) and Au(111) surfaces. But when heated at higher O 2 pressures, the oxide phase depends on the substrate. We found that CoO x /Pt is more active for the CO oxidation reaction than CoO x /Au, even when both surfaces stabilize the same oxide phase. DFT calculations on these and related noble-metal-supported CoO x films reveal an SMSI-induced reactivity enhancement that strongly depends on the oxide film thickness and which is mediated by charge transfer between the metal and oxide. Charge transfer is also found to correlate with the reaction energy and activation barrier for CO oxidation. This effect was found to be greatest for oxide films on Pt, decreasing on other noble metal supports in the order Pt > Pd > Au > Ag, in agreement with the experiments. The role of charge transfer in the activation barriers and reaction energies provides insight into the nature of SMSI-induced catalytic activity, and suggests that the noble metal work function can serve as an indicator for the strength of SMSI effects.

36 MATERIALS SCIENCE↗

Unraveling Enhanced Superconductivity in Single-Layer FeSe through Substrate Surface Terminations

Single-layer FeSe on SrTiO 3 (001) substrates shows a superconducting transition temperature much higher than that of bulk FeSe, which has been attributed to factors such as electron doping, interfacial electron–phonon coupling, and electron correlations. To pinpoint the primary driver, we grew single-layer FeSe films on SrTiO 3 (001) substrates with coexisting TiO 2 and SrO surface terminations. Scanning tunneling spectroscopy revealed a larger superconducting gap (17.0 meV) on the TiO 2 -termination than on the SrO-termination (10.5 meV). Tunneling spectroscopy also showed a larger work function on the SrO surface, resulting in reduced charge transfer to FeSe, as confirmed by angle-resolved photoemission spectroscopy. Scanning transmission electron microscopy further revealed distinctive interfacial atomic-scale structures, with the Se–Fe–Se tetrahedral angle changing from 109.5° on the SrO-termination to 104.9° on the TiO 2 -termination. Compared to dynamical mean field theory calculations, our results indicate that enhanced superconductivity in single-layer FeSe/TiO 2 arises from optimal electron correlations, in addition to sufficient charge transfer from the substrate.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Unraveling the Mechanism of Interfacial Charge Transfer and Photoresponsivity of WS 2 Quantum Dots/MoS 2 (0D–2D) Heterostructure-Based Transistors

To assess the efficacy of a mixed-dimensional van der Waals (vdW) heterostructure in modulating the optoelectronic responses of nanodevices, the charge transport properties of the transition-metal dichalcogenide (TMD)-based heterostructure comprising zero-dimensional (0D) WS 2 quantum dots (QDs) and two-dimensional (2D) MoS 2 flakes are critically analyzed. Herein, a facile strategy was materialized in developing an atomically thin phototransistor assembled from mechanically exfoliated MoS 2 and WS 2 QDs synthesized using a one-pot hydrothermal route. The amalgamated photodetectors exhibited a high responsivity of ∼8000 A/W at an incident power of 0.05 nW of white light, surpassing that of the pristine MoS 2 devices. Furthermore, the detectivity of pristine MoS 2 , which was on the order of 10 10 , increased to 10 12 Jones for the WS 2 QDs/MoS 2 heterostructure photodetector, outperforming other WS 2 -based materials. The quasiparticle band gap and density of states (DOS) are further analyzed to elucidate the photophysics of the WS 2 QD/MoS 2 hybrid assembly. The difference in the work function between MoS 2 and WS 2 QDs gives rise to an electric field across the 0D–2D interface, facilitating effective charge separation and migration and contributing to the enhancement of photoresponsivity. The analysis of optical responses using density functional theory (DFT) revealed stronger absorption and less reflection over a broader spectrum of wavelengths for the heterostructure compared to the pristine materials. The estimated optical conductivity aligns well with the experimentally predicted maximum photoresponsivity under visible light, which is attributed to the high absorbance of 2D MoS 2 . In conclusion, combining diverse spectroscopic and imaging techniques with quantum simulation provides insights that clarify the pertinence of 0D–2D TMDs in designing phototransistors.

WS2 QDs/MoS2 heterostructure↗

Deposition-Dependent Coverage and Performance of Phosphonic Acid Interface Modifiers in Halide Perovskite Optoelectronics

In this work, we study the effect of various deposition methods for phosphonic acid interface modifiers commonly pursued as self-assembled monolayers in high-performance metal halide perovskite photovoltaics and light-emitting diodes. We compare the deposition of (2-(3,6-diiodo-9H-carbazol-9-yl)ethyl)phosphonic acid onto indium tin oxide (ITO) bottom contacts by varying three parameters: the method of deposition, specifically spin coating or prolonged dip coating; ITO surface treatment via HCl/FeCl3 etching; and use in combination with a second modifier, 1,6-hexylenediphosphonic acid. We demonstrate that varying these modification protocols can impact time-resolved photoluminescence carrier lifetimes and quasi-Fermi level splitting of perovskite films deposited onto the phosphonic acid-modified ITO. Ultraviolet photoelectron spectroscopy shows an increase in the effective work function after phosphonic acid modification and clear evidence for photoemission from carbazole functional groups at the ITO surface. We used X-ray photoelectron spectroscopy to probe differences in phosphonic acid coverage on the metal oxide contact and show that perovskite samples grown on ITO with the highest phosphonic acid coverage exhibit the longest carrier lifetimes. Finally, we establish that device performance follows these same trends. These results indicate that the reactivity, heterogeneity, and composition of the bottom contact help to control recombination rates and therefore power conversion efficiencies. ITO etching, prolonged deposition times for phosphonic acids via dip coating, and the use of a secondary, more hydrophilic bisphosphonic acid all contribute to improvements in surface coverage, carrier lifetime, and device efficiency. Furthermore, these improvements each have a positive impact, and we achieve the best results when all three strategies are implemented.

contact engineering↗

Structure of Layers Formed by [2-(3,6-Disubstituted-9 H -carbazol-9-yl)ethyl]phosphonic Acids on Metal Oxides

[2-(9 H -Carbazol-9-yl)ethyl]phosphonic acid (2PACz) and its derivatives are being used extensively as hole-transport layers in organic and perovskite solar cells due to their ability to modify electrode work function, surface wettability, and in some cases, to improve active-layer adhesion, while minimizing interfacial energy losses. The orientation and coverage of surface modifiers significantly impact these functional properties; however, the detailed structure and packing in these overlayers are challenging to investigate, leading to a lack of understanding of how this structure and packing influence performance and limiting the ability to rationally design molecular modifiers. Here, we investigate monolayers of 2-(9 H -carbazol-9-yl)ethyl phosphonic acid derivatives (from here on referred to as X-2PACz) on indium tin oxide (ITO) and alpha phase aluminum oxide (α-Al 2 O 3 ) using a combination of X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and X-ray reflectivity (XRR). By correlating elemental ratios, molecular orientation, and electron density profiles, we directly quantify surface coverage, layer thickness, and molecular tilt across a series of chemically related monolayers. We find that 2PACz and the X-2PACz derivatives form dense monolayers on α-Al 2 O 3 and ITO, with similar surface coverages on either substrate that are inversely proportional to molecular steric bulk. These surface coverage results indicate that X-2PACz is sterically limited in its monolayer surface packing density, as opposed to site limited. Despite surface packing density differences between molecules, the NEXAFS data show a constant average molecular orientation of 61° to 65° between the plane of the carbazole and the substrate for all the molecules on both substrates. These results increase our general understanding of 2PACz derivatives as they become increasingly useful in high performance solar cells.

NEXAFS↗

Modulating Mid-Gap Electronic States Through Site-Selective Modification in B-Pbx/B'-CuyV2O5/CdS Heterostructures for Photocatalytic Hydrogen Evolution

We interfaced ..beta..-Pbx/..beta..'-CuyV2O5 compounds, with varying stoichiometries of precisely positioned Pb-ions (x) and Cu-ions (y) in interstitial sites along a tunnel-structured ?-V2O5 framework, with cysteine-capped CdS (cysCdS) quantum dots (QDs) to yield heterostructured photocatalysts. ..beta..-Pbx/..beta..'-CuyV2O5 compounds exhibit midgap electronic states with orbital contributions from both Cu 3d and stereochemically active Pb 6s states that show distinctive light-initiated reactivity with photoexcited QDs. ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures were prepared by linker-assisted assembly (LAA). Scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy revealed that cysCdS QDs were deposited onto surfaces of ..beta..-Pbx/..beta..'-CuyV2O5 via LAA. HAXPES revealed that the site-selective positioning of Pb-ions and Cu-ions promoted close energetic alignment of the midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds with the valence-band maximum of cysCdS QDs. Transient absorption spectroscopy revealed that photogenerated holes were transferred from CdS QDs to midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds on time scales <50 ps. Finally, photoelectrochemical and photochemical experiments revealed that ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the photocatalytic reduction of H+ to H2. In photoelectrochemical experiments, under oxidative conditions, for all ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at a Pt counter electrode while a sacrificial donor was oxidized at the heterostructure-functionalized working electrode. In contrast, under reductive conditions, for ..beta..-Pb0.152V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at the working electrode. In photochemical experiments, dispersed ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the reduction of H+ to H2 under white-light illumination; ..beta..'-Cu0.55V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, for which midgap states have Cu 3d orbital character, generated 2-fold more H2 than ..beta..-Pb0.152V2O5/CdS heterostructures. Cu-ion insertion thus appends additional acceptor surface states that improve ligand-mediated hole transfer from photoexcited QDs, but such states are intrinsically limited in mediating hole transport to the substrate as a result of the low mobility of holes in narrow Cu 3d-states. Our results reveal that the density and orbital character of midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds, tunable through recently developed site-selective ion insertion strategies, determine efficiencies of charge-transfer and charge-transport mechanisms that underpin photocatalysis.

36 MATERIALS SCIENCE↗

Remote-Contact Catalysis for Target-Diameter Semiconducting Carbon Nanotube Arrays

Electrostatic catalysis has been an exciting development in chemical synthesis (beyond enzymes catalysis1 ) in recent years, boosting reaction rates and selectively producing certain reaction products2 . Most of the studies to date have been focused on using external electric field (EEF) to rearrange the charge distribution in small molecule reactions such as Diels-Alder addition3 , carbene reaction4 , etc. However, in order for these EEFs to be effective, a field on the order of 1 V/nm (10 MV/cm) is required, and the direction of the EEF has to be aligned with the reaction axis5 . Such a large and oriented EEF will be challenging for large-scale implementation, or materials growth with multiple reaction axis or steps. Here, we demonstrate that the energy band at the tip of an individual single-walled carbon nanotube6 (SWCNT) can be spontaneously shifted in a high-permittivity growth environment, with its other end in contact with a low-work function electrode (e.g., hafnium carbide or titanium carbide7 ). By adjusting the Fermi level at a point where there is a substantial disparity in the density of states (DOS) between semiconducting (s-) and metallic (m-) SWCNTs8 , we achieve effective electrostatic catalysis for s-SWCNT growth assisted by a weak EEF perturbation (200V/cm). This approach enables the production of high-purity (99.92%) s-SWCNT horizontal arrays with narrow diameter distribution (0.95±0.04 nm), targeting the requirement of advanced SWCNT-based electronics for future computing9-11. These findings highlight the potential of electrostatic catalysis in precise materials growth, especially for s-SWCNTs, and pave the way for the development of advanced SWCNT-based electronics12.

Wang, Jiangtao↗

Memsensing by surface ion migration within Debye length

Integration between electronics and biology is often facilitated by iontronics, where ion migration in aqueous media governs sensing and memory. However, the Debye screening effect limits electric fields to the Debye length, the distance over which mobile ions screen electrostatic interactions, necessitating external voltages that constrain the operation speed and device design. Here we report a high-speed in-memory sensor based on vanadium dioxide (VO2) that operates without an external voltage by leveraging built-in electric fields within the Debye length. When VO2 contacts a low-work-function metal (for example, indium) in a salt solution, electrochemical reactions generate indium ions that migrate into the VO2 surface under the native electric field, inducing a surface insulator-to-metal phase transition of VO2. The VO2 conductance increase rate reflects the salt concentration, enabling in-memory sensing, or memsensing of the solution. The memsensor mimics Caenorhabditis elegans chemosensory plasticity to guide a miniature boat for adaptive chemotaxis, illustrating low-power aquatic neurorobotics with fewer memory units.

Guo, Ruihan↗