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Characterization of electron spin polarization from positive electron affinity GaAs photocathodes

Negative Electron Affinity (NEA) GaAs photocathodes are widely used to generate spin-polarized electron beams, typically achieving Electron Spin Polarizations (ESPs) in the range of 35%–40%. However, when operated in a Positive Electron Affinity (PEA) state, where a potential barrier inhibits low-energy electrons from escaping into vacuum, measured ESPs can exceed 50%. This effect can occur naturally during photocathode operation, as the NEA surface activation layers can degrade easily over time, increasing the electron affinity. In this work, we investigate and characterize the behavior of enhanced ESPs under PEA conditions. We present experimental measurements of ESP using a retarding-field Mott polarimeter on GaAs photocathodes with controlled and varying electron affinities. These results are complemented by theoretical explanations considering the material band structure, the light excitation profile, and spin depolarization mechanisms.

Electronic band structure

Nb 2 O 5 Protection Layers for Hydrogen Evolution by p-InP Photocathodes in Acidic Electrolytes

Coatings of HfO 2 , Ta 2 O 5 , TiO 2 , and Nb 2 O 5 were evaluated as protection layers for p-InP photocathodes in aqueous acidic electrolytes. Each candidate protection layer was characterized based on interfacial conduction of photogenerated electrons, the thermodynamic and kinetic stability of the overlayer over the relevant potential and pH range for cathodic fuel-forming half-reactions, and inhibition of the primary anodic and/or chemical dissolution processes that limit electrode stability. The conduction of photogenerated electrons and inhibition of anodic oxidation was evaluated using V 3+ / 2+ in 5.0 M HCl(aq) as a one-electron redox couple with a potential close to that of hydrogen evolution in acidic media. Failure modes due to cathodic plating of metal, as well as anodic dissolution and chemical dissolution processes, were evaluated for photocathodes made from etched p-InP, platinized p-InP, and p-InP photoelectrodes that had been coated with the various oxide films and then platinized for use in photoelectrochemical hydrogen evolution in acidic aqueous electrolytes. Nb 2 O 5 best met all of the criteria, contrasting with TiO 2 , which is thermodynamically and kinetically unstable in acid over the potential range relevant for the hydrogen evolution and/or CO 2 reduction electrochemical half-reactions. Furthermore, these protocols should be useful for other materials and semiconductors to determine the effectiveness of protection layers for photocathodes.

Electrodes

Photoelectron Spectroscopic Determination of the Interfacial Energetics of Metal Oxide Protection Layers on p-InP Photocathodes

The interfacial energetics between p-type InP and a series of metal oxides, including TiO 2 , Nb 2 O 5 , Ta 2 O 5 , and HfO 2 , were evaluated using X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and optical absorption spectroscopy. The energy of the conduction-band minimum ( E cb ) of TiO 2 and Nb 2 O 5 was more negative (i.e., further from the vacuum level) than the conduction-band minimum at the surface of InP ( E cb,s ), whereas E cb for Ta 2 O 5 and HfO 2 was more positive than E cb,s for InP. The data are consistent with the electrochemical behavior of p-InP coated with various metal oxide candidate protection layers, with TiO 2 and Nb 2 O 5 facilitating interfacial transfer of photogenerated minority-carrier electrons in p-InP photocathodes, and Ta 2 O 5 and HfO 2 blocking photogenerated electrons in p-InP from readily transferring across the oxide-coated photocathodes. The energy of the valence-band maximum ( E vb ) for all of the oxides was much more negative than E vb,s for InP, consistent with observations that these protection layers effectively block hole transport and consequently suppress oxidative degradation of the underlying p-InP photocathodes.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN

Surface Composition Impacts Selectivity of ZnTe Photocathodes in Photoelectrochemical CO 2 Reduction Reaction

Light-driven reduction of CO 2 into chemicals using a photoelectrochemical (PEC) approach is considered as a promising way to meet the carbon neutral target. The very top surface of the photoelectrode and semiconductor/electrolyte interface plays a pivotal role in defining the performance for PEC CO 2 reduction. However, such impact remains poorly understood. Here, we report an electrodeposition-annealing route for tailoring surface composition of ZnTe photocathodes. Our work demonstrates that a Zn-rich surface on the ZnTe photocathode is essential to impact the CO 2 reduction activity and selectivity. In particular, the Zn-rich surface not only facilitated the interfacial charge carrier transfer, but also acted as electrocatalyst for boosting carbon product selectivity and suppressing the hydrogen evolution reaction. This work provides a new avenue to optimize the photocathode, as well as improvement of the CO 2 RR performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

First-principles study of structural, elastic, electronic, transport properties, and dielectric breakdown of Cs 2 Te photocathode

The pursuit to operate photocathodes at high accelerating gradients to increase brightness of electron beams is gaining interests within the accelerator community, particularly for applications such as free electron lasers (FEL) and compact accelerators. Cesium telluride (Cs 2 Te) is a widely used photocathode material and it is presumed to offer resilience to higher gradients because of its wider band gap compared to other semiconductors. Despite its advantages, crucial material properties of Cs 2 Te remain largely unknown both in theory and experiments. In this study, we employ first-principles calculations to provide detailed structural, elastic, electronic and transport properties of Cs 2 Te. It is found that Cs 2 Te has an intrinsic mobility of 20 cm 2 /Vs for electrons and 2.0 cm 2 /Vs for holes at room temperature. The low mobility is primarily limited by the strong polar optical phonon scattering. Cs 2 Te also exhibits ultralow lattice thermal conductivity of 0.2 W/(m*K) at room temperature. Based on the energy gain/loss balance under external field and electron–phonon scattering, we predict that Cs 2 Te has a dielectric breakdown field in the range from ~ 60 to ~ 132 MV/m at room temperature dependent on the doping level of Cs 2 Te. Our results are crucial to advance the understanding of applicability of Cs 2 Te photocathodes for high-gradient operation.

36 MATERIALS SCIENCE

Growth of ultra-flat ultra-thin alkali antimonide photocathode films

Ultra-flat, ultra-thin alkali antimonide photocathodes with high crystallinity can exhibit high quantum efficiency and low mean transverse energy of outgoing electrons, which are essential requirements for a variety of applications for photocathode materials. Here, we investigate the growth of Cs 3 Sb on graphene-coated 4H–SiC (Gr/4H–SiC), 3C–SiC, and Si 3 N 4 substrates. Sb is deposited using pulsed laser deposition, while Cs is deposited thermally and simultaneously. We demonstrate, employing x-ray analysis and quantum efficiency measurements, that this growth method yields atomically smooth Cs 3 Sb photocathodes with a high quantum efficiency (>10%), even in the ultra-thin limit (<30 nm). For the Si 3 N 4 substrate, film growth is shown to be polycrystalline, while films grown on Gr/4H–SiC show a high degree of ordering with signs of epitaxy.

36 MATERIALS SCIENCE

Measurement of spin-polarized photoemission from wurtzite and zinc blende gallium nitride photocathodes

Spin-polarized photoemission from wurtzite and zinc blende gallium nitride (GaN) photocathodes has been observed and measured. The p-doped GaN photocathodes were epitaxially grown and activated to negative electron affinity with a cesium monolayer deposited on their surfaces. A field-retarding Mott polarimeter was used to measure the spin polarization of electrons photoemitted from the top of the valence band. A spectral scan with a tunable optical parametric amplifier constructed to provide low-bandwidth light revealed peak spin polarizations of 17% and 29% in the wurtzite and zinc blende photocathodes, respectively. Zinc blende GaN results are analyzed with a spin polarization model accounting for experimental parameters used in the measurements, while possible mechanisms influencing the obtained spin polarization values of wurtzite GaN are discussed.

Physics

Emission properties of a hybrid metallized diamond(001) photocathode

The spectral emission characteristics of a proof-of-concept hybrid metallized diamond(001) photocathode are presented. The quantum efficiency (QE) is shown to be determined by the photoinjection efficiency across the ohmic contact at the back metallized face, whereas the mean transverse energy (MTE) of the photoemitted electrons is consistent with an (optical)phonon-assisted and momentum-resonant Franck-Condon mechanism [Franck-Condon electron emission from polar semiconductor photocathodes, Phys. Rev. Appl. 23, 054065 (2025)] following electron drift transport to the untreated diamond(001) front emission face. Emission is observed from both the lower and upper conduction bands of diamond with positive and negative electron affinity, respectively. A potential route to the realization of a red-visible photocathode based on this concept with a sub-50 meV MTE and a QE greater than 0.1% is discussed.

Density of states

Channel electron multipliers - Detection efficiencies with opaque MgF2 photocathodes at XUV wavelengths

Detection efficiencies of channel electron multipliers (CEM) with opaque MgF2 photocathodes obtained in the extreme ultraviolet (XUV), 44 A to 990 A, are reported. A stable highly efficient response is reported for that interval, with no adverse effects on CEM performance. Efficiencies twice those of uncoated CEMs are obtained for 50 A to 350 A. The Mullard B419BL and Galileo 4510WL single-stage cone-cathode CEMs were used in the experiments. A rare-gas double ionization chamber was employed as absolute standard detector for 406 A to 990 A, and a flow Geiger counter filled with 96% argon and 4% isobutane for 44 A to 256 A. Absolute detection efficiencies are 10% higher from 67 A to 990 A when photocathodes are illuminated at an angle of incidence 45 deg. The photocathodes suffered no loss of response in storage (in vacuum or air) after an initial aging period. Effects of scattered UV radiation are greatly reduced when MgF2-coated CEMs are used in the XUV.

Lapson, L. B.

Buried Interfaces in Organic Photocathodes for H 2 Evolution: Fermi-Level Pinning and Recombination

Herein, we demonstrate how Fermi-level pinning at buried contacts impacts solar fuel generation in all-polymer photocathodes by systematically comparing the effects of work function, hydroxyl coverage, and hydrogen evolution using chemically modified indium tin oxide (ITO) supports. Photovoltages and net photocathode performance are improved when the ITO is passivated using phosphonic acids, independent of work function, suggesting that the passivation reduces Fermi-level pinning at the buried interface arising from blended heterojunction interactions with surface metal hydroxyls. Transient photovoltage decay reveals differences in recombination mechanisms, supported by light intensity-dependent measurements. Briefly, nonpassivated, hydrophilic contacts exhibit trap-assisted recombination, while passivated, hydrophobic contacts follow bimolecular recombination. We then investigate changes in electroactivity of hole-transfer processes as a function of scan rate and repetitive cycling using a diffusion-controlled molecular redox probe, analogous to a hole-only device achieved via the electrolyte. The nonpassivated buried contacts exhibit higher overpotentials for oxidation, indicative of hole injection/extraction barriers. We observe irreversible electron transfer via the hole-transport level of the blended heterojunction and a strong cycle dependence, consistent with changes in the hole trap state density. Passivation results in more reversible redox behaviors, consistent with more Ohmic-like contacts. Collectively, these results provide context toward the realization of durable organic photoelectrodes with optimized photovoltages and net solar-to-hydrogen conversion efficiencies via fundamental understanding of the rates of carrier generation, recombination, and transport in high-dielectric aqueous environments and opportunities to characterize buried interfaces under device-relevant electric fields.

buried interfaces

High-intensity polarized electron gun featuring distributed Bragg reflector GaAs photocathode

The polarized electron source is a critical component in accelerator facilities such as the electron–ion collider, which requires a polarized electron gun with higher voltage and higher bunch charge than existing sources. One challenge we faced was the surface charge limit of the distributed Bragg reflector GaAs/GaAsP superlattice (DBR-SL-GaAs) photocathode. We suppressed this effect by optimizing the surface doping and heat cleaning procedures. We achieved up to 11.6 nC bunch charge of polarized electron beam. In this report, we discuss the performance of tests of a DBR-SL-GaAs photocathode in the high voltage direct current gun. Possible reasons for the observed peak quantum efficiency wavelength shift are analyzed, and we addressed it by using a wavelength tunable laser. In addition, the impact of the DBR layer and laser on the lifetime is investigated in this paper. The optimal DBR-SL-GaAs operating zone has been proposed, which gave us a long lifetime and high polarization at 30 μA operation. Finally, the success of this polarized gun will be key to the future of the nuclear sciences.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS

Characterization of Cs 3 Sb photocathodes at cryogenic temperatures

Here, we report measurements of quantum efficiency (QE) and mean transverse energy (MTE) from Cs 3 Sb photocathodes in a wide range of photon energies at both room and cryogenic temperatures. Our measurements show a strong temperature dependence of MTE even at photon energies well above threshold, indicating the presence of strong inelastic scattering of excited electrons during transport before emission into vacuum. We also demonstrate a cathode cooling method that largely preserves the QE while reducing MTE, allowing us to achieve MTEs as low as 58 meV with 3% QE in green light from Cs 3 Sb photocathodes. Our results are crucial for producing brighter electron beams for various photoinjector applications like ultrafast electron diffraction and microscopy, x-ray free-electron lasers, and particle colliders.

36 MATERIALS SCIENCE

Impact of superlattice size on quantum efficiency and polarization in MOCVD-grown strained GaAs/GaAsP photocathodes

Strained superlattice GaAs photocathodes are crucial for providing high photocurrent beams of spin-polarized electrons at several accelerator facilities including the Continuous Electron Beam Accelerator Facility at Thomas Jefferson National Accelerator Facility and the future Electron–Ion Collider at Brookhaven National Laboratory. Here, in this work, we study the effects of varying the number of superlattice pairs on the polarization and photocurrent of the photocathodes. We observe a saturation in quantum efficiency beyond 30 pairs, with additional layers yielding minimal photocurrent improvement while noticeably reducing the polarization of the beam.

Chemical vapor deposition

Mild-Annealed Molecular Layer Deposition (MLD) Tincone Thin Film as Photoelectrochemically Stable and Efficient Electron Transport Layer for Si Photocathodes

Metalcone thin films, composed of inorganic–organic hybrids, are synthesized using molecular layer deposition (MLD) through reactions between organometallic precursors (e.g., Sn, Al, and Ti) and organic reactants (e.g., ethylene glycol and glycerol). Despite their unique properties, metalcones exhibit significant vulnerability to water due to their organic components, limiting their potential in electrochemical applications. This study focuses on enhancing the photoelectrochemical stability of tincone thin films in aqueous electrolyte while preserving their hybrid characteristics through mild annealing in air at 250 °C. As-deposited and vacuum-annealed tincone thin films exhibited significant degradation under these conditions, while high-temperature-annealed (500 °C) tincone thin films offered improved stability with a significant decline in charge transfer efficiency. In contrast, mild annealing in air maintained the C–O bond at half level and improved the stability and charge transport without compromising the unique characteristics of tincone. This was confirmed by ellipsometry, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). Mild-annealed tincone deposited on a lightly doped p-type silicon (p-Si) photocathode produced a 20-fold increase in CO volume compared to high-temperature annealed tincone in a CO 2 -saturated potassium bicarbonate (KHCO 3 ) electrolyte with dispersed graphene oxide–cobalt phthalocyanine (GO-CoPc) under 1 sun illumination at 0.9 V vs reversible hydrogen electrode (RHE), while maintaining the faradaic efficiency for CO and H 2 . These results suggest that mild-annealed tincone thin films hold significant potential as protective charge transport layers on silicon photocathodes for the aqueous CO 2 reduction reaction (CO 2 RR).

Annealing (metallurgy)

Front-Surface Potential of Platinized p -InP Photocathodes Probed by Dual-Working-Electrode Measurements

The front-surface potential (E fr ) of p-InP/Pt photocathodes performing the hydrogen-evolution reaction has been probed under operating conditions using a dual-workingelectrode (DWE) method. The DWE data are consistent with expectations for proposed stability mechanisms for p-InP photocathodes. Specifically, E fr for Pt-modified p-InP adopts a value near the reversible hydrogen electrode (RHE) potential, consistent with kinetic suppression of metallic In 0 formation. The data provide a rapid, operando metric of interfacial catalyst activity, and indicate that E fr for the p-InP/Pt junction is governed by surface catalytic kinetics rather than by the applied back-contact potential (E b ).

Catalysts

Pulsed laser deposition of delafossite oxide thin films on YSZ (001) substrates as solar water splitting photocathodes

Development of solar energy converters with earth-abundant and environmentally friendly materials is one of the key routes explored towards a sustainable future. In this work, crystalline delafossite-phase CuAlO 2 and CuFeO 2 thin film solar water splitting photocathodes were fabricated using pulsed laser deposition. It was found that the desired delafossite phase was formed only after high temperature annealing in an oxygen-free atmosphere. Further, the homogeneous delafossite bulk structure of the films was determined by correlating simulation results from first-principles calculations with synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy. Both CuAlO 2 and CuFeO 2 photocathodes are active for solar water splitting, with the latter more efficient due to its narrower band gap and improved light absorption.

36 MATERIALS SCIENCE

Recent developments and operation of polarized photocathodes at Jefferson Lab

Spin-polarized electron sources are critical to a wide range of accelerator-based applications for nuclear and particle physics. At Thomas Jefferson National Accelerator Facility, they play a central role in delivering high-quality polarized beams for precision nuclear physics experiments and next-generation parity-violation measurements, where stringent control of systematic uncertainties is essential. These sources are also expected to be key components of other initiatives, including the Electron-Ion Collider and the potential future positron capabilities at Jefferson Lab. In this talk, I will present ongoing research and development efforts at Jefferson Lab focused on the design, fabrication and optimization of spin-polarized photocathodes. This includes growth using molecular beam epitaxy (MBE) or metal-organic chemical vapor deposition (MOCVD), along with detailed characterization of their performance metrics, such as quantum efficiency (QE), electron spin polarization and QE anisotropy, all of which are increasingly important metrics for polarized electron sources at Jefferson Lab and the Electron-Ion Collider. Strategies to mitigate QE anisotropy, which is critical for reducing helicity-correlated beam asymmetries in precision experiments such as MOLLER will be highlighted. Finally, I will present recent efforts aimed at improving the operational lifetime of spin-polarized photocathodes in injector environments, particularly under high-voltage conditions in DC electron guns. These developments are essential for enabling reliable, high-performance operation of polarized sources for current and future accelerator programs.

Kachwala, Alimohammed [Thomas Jefferson National A