Photocathode Surface Research Articles

The influence of surface barriers on the photoemission characteristics of AlGaN photocathodes

In order to research the photoemission characteristics of AlGaN photocathodes with different surface barrier structures, AlGaN photocathodes with varying Al composition were grown by MOCVD. The atomic composition of the photocathode surface was measured by Ar+ ion sputtering and XPS. We find that the C atoms only exist at the surface, but O atoms are present up to 6nm from its surface. The photocathodes were cleaned and activated with different processing methods, and the result show that the quantum efficiency value of Cs/O activated AlGaN photocathodes were about 42% higher than that of Cs-only activated AlGaN photocathode. Through thermal cleaning at 850°C and Cs/O activation, the maximum quantum efficiency of the AlGaN photocathode was 49.39% at 240nm. Through simulation of the electronic energy distribution, we determined that the surface barrier I structure formed by [AlGaN: Mg-Cs] dipoles at the photocathode surface was mainly affecting the surface electrons escapes probability and determining the photocathode quantum efficiency. The surface barrier II structure formed by [Cs-O] dipoles at the photocathode surface determined the photocathode performance, and also affected the electronic energy distribution concentration.

Spectral response characteristics of the transmission-mode aluminum gallium nitride photocathode with varying aluminum composition.

In order to research spectral response characteristics of transmission-mode nanostructure aluminum gallium nitride (AlGaN) photocathodes, the AlGaN photocathodes materials with varied aluminum (Al) composition were grown by metalorganic chemical vapor deposition (MOCVD) and its optical properties were measured. The Al compositions of each AlGaN film of the photocathodes were analyzed from their adsorption properties curves; their thickness was also calculated by the matrix formula of thin-film optics. The nanostructure AlGaN photocathodes were activated with the Caesium-Oxygen (Cs-O) alternation, and after the photocathode was packaged in vacuum, their spectrum responses were measured. The experimental results showed that the trend of spectrum response curves first increased and then decreased along with the increasing of the incident light wavelength. The peak spectrum response value was 17.5mA/W at 255nm, and its quantum efficiency was 8.5%. The lattice defects near the interface of the AlGaN heterostructure could impede the electron motion crossing this region and moving toward the photocathode surface; this was a factor that reduces the electron emission performance of the photocathodes. Also, the experimental result showed that the thickness of each AlGaN layer affected the electron diffusion characteristics; this was a key factor that influenced the spectrum response performance.

Ultraviolet laser transverse profile shaping for improving x-ray free electron laser performance

The photocathode rf gun is one of the most critical components in x-ray free electron lasers. The drive laser strikes the photocathode surface, which emits electrons with properties that depend on the shape of the drive laser. Most free electron lasers use photocathodes with work function in the ultraviolet, a wavelength where direct laser manipulation becomes challenging. In this paper, we present a novel application of a digital micromirror device (DMD) for the 253 nm drive laser at the Linear Coherent Light Source. Laser profile shaping is accomplished through an iterative algorithm that takes into account shaping error and efficiency. Next, we use laser shaping to control the X-ray laser output via an online optimizer, which shows improvement in FEL pulse energy. Lastly, as a preparation for electron beam shaping, we use the DMD to measure the photocathode quantum efficiency across cathode surface with an averaged laser rms spot size of $59\text{ }\text{ }\ensuremath{\mu}\mathrm{m}$. Our experiments demonstrate promising outlook of using DMD to shape ultraviolet lasers for photocathode rf guns with various applications.

Active bialkali photocathodes on free-standing graphene substrates

The hexagonal structure of graphene gives rise to the property of gas impermeability, motivating its investigation for a new application: protection of semiconductor photocathodes in electron accelerators. These materials are extremely susceptible to degradation in efficiency through multiple mechanisms related to contamination from the local imperfect vacuum environment of the host photoinjector. Few-layer graphene has been predicted to permit a modified photoemission response of protected photocathode surfaces, and recent experiments of single-layer graphene on copper have begun to confirm these predictions for single crystal metallic photocathodes. Unlike metallic photoemitters, the integration of an ultra-thin graphene barrier film with conventional semiconductor photocathode growth processes is not straightforward. A first step toward addressing this challenge is the growth and characterization of technologically relevant, high quantum efficiency bialkali photocathodes on ultra-thin free-standing graphene substrates. Photocathode growth on free-standing graphene provides the opportunity to integrate these two materials and study their interaction. Specifically, spectral response features and photoemission stability of cathodes grown on graphene substrates are compared to those deposited on established substrates. In addition, we observed an increase of work function for the graphene encapsulated bialkali photocathode surfaces, which is predicted by our calculations. The results provide a unique demonstration of bialkali photocathodes on free-standing substrates, and indicate promise towards our goal of fabricating high-performance graphene encapsulated photocathodes with enhanced lifetime for accelerator applications.

Large photocathode 20-inch PMT testing methods for the JUNO experiment

The 20 kt Liquid Scintillator (LS) JUNO detector is being constructed by the International Collaboration in China, with the primary goal of addressing the question of neutrino mass ordering (hierarchy). The main challenge for JUNO is to achieve a record energy resolution, ∼ 3% at 1 MeV of energy released in the LS, which is required to perform the neutrino mass hierarchy determination. About 20 000 large 20′′ PMTs with high Photon Detection Efficiency (PDE) and good photocathode uniformity will ensure an approximately 80% surface coverage of the JUNO detector. The JUNO collaboration is preparing equipment for the mass tests of all PMTs using 4 dedicated containers. Each container consists of 36 drawers. Each drawer will test a single PMT. This approach allows us to test 144 PMTs in parallel. The primary measurement in the container will be the PMT response to illumination of its photocathode by a low-intensity uniform light. Each of the 20000 PMTs will undergo the container test. Additionally, a dedicated scanning system was constructed for sampled tests of PMTs that allows us to study the variation of the PDE over the entire PMT photocathode surface. A sophisticated laboratory for PMT testing was recently built. It includes a dark room where the scanning station is housed. The core of the scanning station is a rotating frame with 7 LED sources of calibrated short light flashes that are placed along the photocathode surface covering zenith angles from the top of a PMT to its equator. It allows for the testing of individual PMTs in all relevant aspects by scanning the photocathode and identifying any potential problems. The collection efficiency of a large PMT is known to be very sensitive to the Earth Magnetic Field (EMF), therefore, understanding the necessary level of EMF suppression is crucial for the JUNO Experiment. A dark room with Helmholtz coils compensating the EMF components is available for these tests at a JUNO facility. The Hamamatsu R12860 20′′ PMT is a candidate for the JUNO experiment. In this article the container design and mass-testing method, the scanning setup and scanning method are briefly described and preliminary results for performance test of this PMT are reported.

Study of Cs/NF3 adsorption on GaN (0 0 1) surface

To investigate the optoelectronics properties of Cs/NF3 adsorption on GaN (0 0 1) photocathode surface, different adsorption models of Cs-only, Cs/O, Cs/NF3 adsorption on GaN clean surface were established, respectively. Atomic structures, work function, adsorption energy, E-Mulliken charge distribution, density of states and optical properties of all these adsorption systems were calculated using first principles. Compared with Cs/O co-adsorption, Cs/NF3 co-adsorption show better stability and more decline of work function, which is more beneficial for photoemission efficiency. Besides, surface band structures of Cs/NF3 co-adsorption system exhibit metal properties, implying good conductivity. Meanwhile, near valence band minimum of Cs/NF3 co-adsorption system, more acceptor levels emerges to form a p-type emission surface, which is conductive to the escape of photoelectrons. In addition, imaginary part of dielectric function curve and absorption curve of Cs/NF3 co-adsorption system both move towards lower energy side. This work can direct the optimization of activation process of NEA GaN photocathode.

Enhancement of Charge Separation and Hydrogen Evolution on Particulate La5Ti2CuS5O7 Photocathodes by Surface Modification.

Particulate La5Ti2CuS5O7 (LTC) photocathodes prepared by particle transfer show a positive onset potential of 0.9 V vs RHE for the photocathodic current in photoelectrochemical (PEC) H2 evolution. However, the low photocathodic current imposes a ceiling on the solar-to-hydrogen energy conversion efficiency of PEC cells based on LTC photocathodes. To improve the photocurrent, in this work, the surface of Mg-doped LTC photocathodes was modified with TiO2, Nb2O5, and Ta2O5 by radio frequency reactive magnetron sputtering. The photocurrent of the modified Mg-doped LTC photocathodes was doubled because these oxides formed type-II heterojunctions and extended the lifetimes of photogenerated charge carriers. The enhanced photocathodic current was attributed to hydrogen evolution at a positive potential of +0.7 V vs RHE. This work opens up possibilities for improving PEC hydrogen evolution on particulate photocathodes based on surface oxide modifications and also highlights the importance of the band gap alignment.

Study of cesium and oxygen adsorption on surface of GaAlAs photocathode in ultra-high vacuum chamber

The mechanism of cesium (Cs) and oxygen (O) adsorption on GaAlAs photocathode has been investigated. The models of Cs and O adsorption on GaAlAs surface are studied, and the electron affinity changing with Cs coverage on GaAlAs surface is calculated based on Topping model. The experiments of Cs activation on GaAlAs and GaAs are performed, and the Cs, O activation experiments with different heat cleaning temperatures are performed on GaAlAs photocathodes. The photocurrent and spectral response curves in the experiments are measured and analyzed. The results show that the Topping calculation of electron affinity changing with Cs coverage on GaAlAs surface is in consistent with the result of experiment, and the electron affinity nearly reaches the bottom of conduction band after the Cs activation. The GaAlAs phtocathode treated by 700°C heat cleaning could obtain a good photoemission performance after Cs, O activation.

Photo-electrocatalytic hydrogen generation at dye-sensitised electrodes functionalised with a heterogeneous metal catalyst

Dye-sensitised photocathodes promoting hydrogen evolution are usually coupled to a catalyst to improve the reaction rate. Herein, we report on the first successful integration of a heterogeneous metal particulate catalyst, viz., Pt aggregates electrodeposited from acidic solutions on the surface of a NiO-based photocathode sensitised with a p-type perylenemonoimid-sexithiophene-triphenylamine dye (PMI-6T-TPA). The platinised dye-NiO electrodes generate photocurrent density of ca −0.03mA cm−2 (geom.) with 100% faradaic efficiency for the H2 evolution at 0.059 V vs. reversible hydrogen electrode under 1 sun visible light irradiation (AM1.5G, 100mWcm−2, λ>400nm) for more than 10hours in 0.1M H2SO4 (aq.). The Pt-free dye-NiO and dye-free Pt-modified NiO cathodes show no photo-electrocatalytic hydrogen evolution under these conditions. The performance of these Pt-modified PMI-6T-TPA-based photoelectrodes compares well to that of previously reported dye-sensitised photocathodes for H2 evolution.

Theoretical study for heterojunction surface of NEA GaN photocathode dispensed with Cs activation

For the disadvantages of conventional negative electron affinity (NEA) GaN photocathodes activated by Cs or Cs/O, new-type NEA GaN photocathodes with heterojunction surface dispensed with Cs activation are investigated based on first-principle study with density functional theory. Through the growth of an ultrathin [Formula: see text]-type GaN cap layer on [Formula: see text]-type GaN emission layer, a [Formula: see text]–[Formula: see text] heterojunction is formed on the surface. According to the calculation results, it is found that Si atoms tend to replace Ga atoms to result in an [Formula: see text]-type doped cap layer which contributes to the decreasing of work function. After the growth of [Formula: see text]-type GaN cap layer, the atom structure near the [Formula: see text]-type emission layer is changed while that away from the surface has no obvious variations. By analyzing the E-Mulliken charge distribution of emission surface with and without cap layer, it is found that the positive charge of Ga and Mg atoms in the emission layer decrease caused by the cap layer, while the negative charge of N atom increases. The conduction band moves downwards after the growth of cap layer. Si atom produces donor levels around the valence band maximum. The absorption coefficient of GaN emission layer decreases and the reflectivity increases caused by [Formula: see text]-type GaN cap layer.

(Invited) Electrochemical and Photoelectrochemical Reduction of Carbon Dioxide: The Twain Shall Meet at Copper Oxide/Copper Nanocube/Liquid Interfaces

Of the myriad electrode materials that have been used for the electrochemical (EC) and photoelectrochemical (PEC) reduction of carbon dioxide in aqueous media, copper oxide/copper interfaces have shown a remarkable range of hydrocarbon and oxygenated products including acids, aldehydes, ketones, and alcohols. This talk highlights experimental evidence for the fact that both EC and PEC reduction scenarios have similar morphological underpinnings in the in situ formation of copper nanocubes on the (photo)cathode surface. Recent rapid developments in our fundamental understanding of these interfaces and areas requiring further studies are discussed in the light of recent studies in the authors’ laboratories and elsewhere.

Electro- and Photoreduction of Carbon Dioxide: The Twain Shall Meet at Copper Oxide/Copper Interfaces

Of the myriad electrode materials that have been used for electrochemical (EC) and photoelectrochemical (PEC) reduction of carbon dioxide in aqueous media, copper oxide/copper interfaces have shown a remarkable range of hydrocarbon and oxygenated products including acids, aldehydes, ketones, and alcohols. This Perspective highlights experimental evidence for the fact that both EC and PEC reduction scenarios have similar chemical and morphological underpinnings in the in situ formation of copper nano- or microcubes on the (photo)cathode surface. Recent rapid developments in our fundamental understanding of these interfaces and areas requiring further studies are discussed in light of recent studies in the authors’ laboratories and elsewhere.

Simultaneous enhancement of photovoltage and charge transfer in Cu2O-based photocathode using buffer and protective layers

Coating n-type buffer and protective layers on Cu2O may be an effective means to improve the photoelectrochemical (PEC) water-splitting performance of Cu2O-based photocathodes. In this letter, the functions of the buffer layer and protective layer on Cu2O are examined. It is found that a Ga2O3 buffer layer can form a buried junction with Cu2O, which inhibits Cu2O self-reduction as well as increases the photovoltage through a small conduction band offset between the two semiconductors. The introduction of a TiO2 thin protective layer not only improves the stability of the photocathode but also enhances the electron transfer from the photocathode surface into the electrolyte, thus resulting in an increase in photocurrent at positive potentials. These results show that the selection of overlayers with appropriate conduction band positions provides an effective strategy for obtaining a high photovoltage and high photocurrent in PEC systems.

Photoemission simulation for photocathode design: theory and application to copper and silver surfaces

Obtaining a bright and low emittance electron beam directly from the photocathode is mandatory in order to design high performance free electron lasers (FELs). To achieve this goal a clear understanding of how the emission process is influenced by structure, morphology and composition of the photocathode surface is needed. This is difficult from an experimental point of view because often the atomic scale details of the surface whose emission has been measured are unknown. A predictive theoretical approach capable of determining the effects of surface structure on emission is therefore or great interest. A model to extend the well known three step model (as proposed by Berglund and Spicer) to surface calculations is discussed in this paper. It is based on a layer-by-layer decomposition of the surface electronic structure that can be calculated through reliable and efficient DFT calculations. The advantage of this approach with respect to other existing photoemission calculations is being able to correlate directly the photoemission to the electronic, atomic and chemical structure of the surface. The proposed approach retains, therefore, the simple chemical intuition in the study of surface modifications and their effect on the photoemission. The approach is validated in calculations of the emission from clean copper and silver surfaces. The ability of the model to simulate the change in photoemission in response to adsorbates is tested by simulating monolayers of oxygen, hydrogen and lithium on the copper (111) surface.

GaN(Mg)-Cs]:[O-Cs] model for the Negative Electron Affinity GaN (0001) surface

Because of the limitations of the existing Negative Electron Affinity (NEA) photocathode surface emission models, [GaN(Mg)-Cs]:[O-Cs] photoemission model based on dual-dipole model is established, which can explain the photoemission mechanism of the NEA GaN photocathode well. Cs, O adsorption process on the GaN (0001) surface during the activation is discussed, and the GaN(Mg)-Cs dipole layer is found having a unified direction which is conducive for photoelectron escaping, so photocurrent has a significant increase when Cs is introduced. There is not a unified direction for the O-Cs dipole layer. Because of the surface defects, part of the O-Cs dipoles have the direction which is conducive for photoelectron escaping, and the photocurrent has a modest growth after introducing O. Finally, the performance of GaN and GaAs photocathode are compared based on the photoemission model, and the reason of better stability of NEA GaN photocathode is interpreted.

Lifetime of MCP-PMTs

The hadron identification in the PANDA experiment at FAIR will be done with DIRC detectors. Because of design and space reasons the sensors of the DIRCs have to be placed inside the strong magnetic field of the solenoid. As the favored photon sensors microchannel-plate photomultipliers (MCP-PMTs) were identified. However, these devices showed serious aging problems until very recently, which manifest themselves by a fast degrading quantum efficiency (QE) of the photo cathode (PC). This is mainly due to feedback ions from the residual gas. In this paper we discuss the recently accomplished huge improvements in the lifetime of MCP-PMTs. With innovative countermeasures applied to the MCP-PMTs in the attempt to reduce the aging effects the manufacturers were able to increase the lifetime of MCP-PMT prototypes by almost two orders of magnitude compared to the former commercially available devices. Our group has studied the aging of MCP-PMTs for more than four years by simultaneously illuminating different types of lifetime-enhanced MCP-PMTs at the same photon rate. Gain, dark count rate, and QE as a function of the wavelength and the PC surface were measured in regular time intervals and studied in dependence of the integrated anode charge. We observe that MCP-PMTs treated with an atomic layer deposition (ALD) technique are by far the best devices available now. A lifetime of up to 10 C/cm2 integrated anode charge was reached with these sensors. This is sufficient for both PANDA DIRCs.

Covalent Immobilization of a Molecular Catalyst on Cu2O Photocathodes for CO2 Reduction.

Sunlight-driven CO2 reduction is a promising way to close the anthropogenic carbon cycle. Integrating light harvester and electrocatalyst functions into a single photoelectrode, which converts solar energy and CO2 directly into reduced carbon species, is under extensive investigation. The immobilization of rhenium-containing CO2 reduction catalysts on the surface of a protected Cu2O-based photocathode allows for the design of a photofunctional unit combining the advantages of molecular catalysts with inorganic photoabsorbers. To achieve large current densities, a nanostructured TiO2 scaffold, processed at low temperature, was deposited on the surface of protected Cu2O photocathodes. This led to a 40-fold enhancement of the catalytic photocurrent as compared to planar devices, resulting in the sunlight-driven evolution of CO at large current densities and with high selectivity. Potentiodynamic and spectroelectrochemical measurements point toward a similar mechanism for the catalyst in the bound and unbound form, whereas no significant production of CO was observed from the scaffold in the absence of a molecular catalyst.

Effect of surface cleaning on spectral response for InGaAs photocathodes.

Photocathode surface treatment aims to obtain high sensitivity, where the key point is to acquire an atomically clean surface. Various surface cleaning methods for removing contamination from InGaAs photocathode surfaces were investigated. The atomic compositions of InGaAs photocathode structures and surfaces were measured by x-ray photoelectron spectroscopy and Ar ion sputtering. After surface cleaning, the InGaAs surface is arsenoxide-free, however, a small amount of Ga2O3 and In2O3 still can be found. The 1:1 mixed solution of hydrochloric acid to deionized water followed by thermal annealing at 525°C has been demonstrated to be the best choice in dealing with the surface oxides. After the Cs/O activation, a surface model was proposed where the oxides on the surface will lead to a positive electron affinity, adversely affecting low-energy electrons escaping to the vacuum, which is reflected by the photocurrent curves and the spectral response curves.

Measurement of the tradeoff between intrinsic emittance and quantum efficiency from a NaKSb photocathode near threshold

We measure the tradeoff between the quantum efficiency and intrinsic emittance from a NaKSb photocathode at three increasing wavelengths (635, 650, and 690 nm) at or below the energy of the bandgap plus the electron affinity, hν≤Eg+Ea. These measurements were performed using a high voltage dc gun for varied photocathode surface fields of 1.4−4.4 MV/m. Measurements of intrinsic emittance are performed using two different methods and were found to agree. At the longest wavelength available, 690 nm, the intrinsic emittance was 0.26 μm/mm-rms with a quantum efficiency of ∼10−4. The suitability of NaKSb emitting at threshold for various low emittance applications is discussed.

Carbon nitride nanosheets sensitized quantum dots as photocathode for photoelectrochemical biosensing

Abstract A highly efficient photocathode, based on graphite-like carbon nitride nanosheets (CNNS) sensitized CdTe quantum dots (QDs), was constructed for photoelectrochemical (PEC) biosensing. Using dissolved oxygen as an electron acceptor, the hybrid photocathode showed a sensitive photocurrent response at −0.2 V bias potential under 405 nm illumination. The CdTe/CNNS hybrid photocathode demonstrates about 100% increase of photocurrent compared to CdTe QDs modified electrode owing to the formation of heterojunction through contact of two semiconductor materials. The improved charge separation efficiency was identified by the extension of electron transit time ( τ d ) and electron lifetime ( τ n ) in this PEC system. The introduction of Cu 2+ on the surface of hybrid photocathode could decrease photocurrent via the exciton trapping quenching effect. A sensitive PEC sensor for Cu 2+ was thus developed with a good linear range from 20 nM to 100 μM and a detection limit of 3.3 nM, and was successfully applied in the detection of Cu 2+ in human hair samples. The CNNS-sensitized photocathode provides a good alternative for enhancement of the PEC signal transduction and could be widely used in biosensing and clinical diagnosis.