Stoichiometry control and automated growth of alkali antimonide photocathode films by molecular beam deposition
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Alkali antimonide photocathodes have wide applications in free-electron lasers and electron cooling. The short lifetime of alkali antimonide photocathodes necessitates frequent replacement of the photocathodes during a beam operation. Furthermore, exposure to mediocre vacuum causes loss of photocathode quantum efficiency due to the chemical reaction with residual gas molecules. Theoretical analyses have shown that covering an alkali antimonide photocathode with a monolayer graphene or hexagonal boron nitride protects it in a coarse vacuum environment due to the inhibition of chemical reactions with residual gas molecules. Alkali antimonide photocathodes require an ultra-high vacuum environment, and depositing a monolayer 2D material on it poses a serious challenge. In the present work, we have incorporated a novel method known as intercalation, in which alkali atoms pass through the defects of a graphene thin film to create a photocathode material underneath. Initially, Sb was deposited on a Si substrate, and a monolayer graphene was transferred on top of the Sb film. Heat cleaning around 550–600 °C effectively removed the Sb oxides, leaving metallic Sb underneath the graphene layer. Depositing Cs on top of a monolayer graphene enabled the intercalation process. Atomic force microscopy, Raman spectroscopy, x-ray photoelectron spectroscopy, low energy electron microscopy, and x-ray diffraction measurements were performed to evaluate photocathode formation underneath the monolayer graphene. Our analysis shows that Cs penetrated the graphene and reacted with Sb and formed Cs 3 Sb.
2D materials showcase unconventional properties emerging from quantum confinement effects. In this work, a “soft chemical” route allows for the deintercalation of K + from the layered antimonide KV 6 Sb 6 , resulting in the discovery of a new metastable 2D-Kagome antimonide K 0.1(1) V 6 Sb 6 with a van der Waals gap of 3.2 Å. The structure of K 0.1(1) V 6 Sb 6 was determined via the synergistic techniques, including X-ray pair distribution function analysis, advanced transmission electron microscopy, and density functional theory calculations. The K 0.1(1) V 6 Sb 6 compound crystallizes in the monoclinic space group C2/m (a = 9.57(2) Å, b = 5.502(8) Å, c = 10.23(2) Å, β = 97.6(2)°, Z = 2). The [V 6 Sb 6 ] layers in K 0.1(1) V 6 Sb 6 are retained upon deintercalation and closely resemble the layers in the parent compound, yet deintercalation results in a relative shift of the adjacent [V 6 Sb 6 ] layers. The magnetic properties of the K 0.1(1) V 6 Sb 6 phase in the 2–300 K range are comparable to those of KV 6 Sb 6 and another Kagome antimonide KV 3 Sb 5 , consistent with nearly temperature-independent paramagnetism. Electronic band structure calculation suggests a nontrivial band topology with flat bands and opening of band crossing afforded by deintercalation. Transport property measurements reveal a metallic nature for K 0.1(1) V 6 Sb 6 and a low thermal conductivity of 0.6 W K –1 m –1 at 300 K. Additionally, ion exchange in KV 6 Sb 6 via a solvothermal route leads to a successful partial exchange of K + with A + (A = Na, Rb, and Cs). Here, this study highlights the tunability of the layered structure of the KV 6 Sb 6 compound, providing a rich playground for the realization of new 2D materials.
Alkali antimonide semiconductor photocathodes are promising candidates for high-brightness electron sources for advanced accelerators, including free-electron lasers (FEL), due to their high quantum efficiency (QE), low emittance, and high temporal resolution. Two challenges with these photocathodes are (1) the lack of a universal deposition recipe to achieve crystal stoichiometries and (2) their high susceptibility to vacuum contamination, which restricts their operation pressure to ultrahigh vacuums and leads to a short lifetime and low extraction charge. To resolve these issues, it is essential to understand the elemental compositions of deposited photocathodes and correlate them to robustness. Here, we report depth profiles for potassium cesium antimonide photocathodes, which were investigated using synchrotron radiation x-ray photoelectron spectroscopy, and the robustness of those photocathodes. We prepared two types of photocathodes with different potassium contents via sequential thermal evaporation. Depth profiles revealed that the photocathodes with a potassium deficit had excess cesium at the surface, while the ratio of potassium and cesium to antimony decreased rapidly within the film. In contrast, the photocathodes with sufficient potassium had close to the theoretical stoichiometry of K 2 CsSb at the surface and maintained that stoichiometry for over half the entire film thickness. Both photocathode types had a similar maximum QE at 532 nm; however, exposure to oxygen revealed that the photocathode with a crystalline stoichiometry of K 2 CsSb maintained QE at one order of magnitude higher pressure compared to its potassium-deficit counterpart. These results highlight the importance of synthesizing potassium cesium antimonide photocathodes with sufficient potassium to achieve the theoretical crystalline stoichiometry for both high QE and improved robustness.
We report on the novel use of a Cs+ ion gun for an ion-beam-assisted molecular-beam-epitaxy (IBA-MBE) method to sequentially deposit Cs-Sb cathodes on room temperature substrates as opposed to the standard technique of thermal evaporation on elevated-temperature substrates. The details of the ultrahigh-vacuum chamber, the Cs+ ion source, and the growth technique are elaborated. The final quantum efficiency (QE) is reasonably good for Cs-Sb cathodes grown on two different substrates—Si (100) and strontium titanate—and is comparable to the QE of cathodes grown using thermal sources. This suggests that IBA-MBE could be a viable alternative to grow alkali-antimonides without substrate heating, paving the way for the growth of epitaxial alkali-antimonides in a more reproducible fashion, which may help improve the efficiency of photon detectors and accelerator applications that use alkali-antimonides as electron sources.
Specific structural motifs in inorganic solids are often related to their targeted physical properties. For many classes of solids, such as Zintl phases and polar intermetallics, the crystal structures are diverse and not easy to predict. Various antimonides that are potential thermoelectric materials were proposed to be synthesizable on the basis of their estimated formation energies. Their structures were broadly classified as clathrate, channel, layered, or network through a machine learning model trained on existing ternary phases and features based on elemental properties using the sure independence screening and sparsifying operator algorithm. Through experimental validation, three new ternary antimonides were synthesized and confirmed to form layered structures: tetragonal RbAlSb 2 and CsAlSb 2 , which are isopointal but not isotypic to LiBSi 2 ; and monoclinic Rb 2 Al 2 Sb 3 , which adopts the Na 2 Al 2 Sb 3 -type structure. Finally, reinvestigation of the related compound Cs 2 In 2 Sb 3 revealed a low thermal conductivity and p-type semiconducting behavior.
We present measurements of enhanced quantum efficiency (QE) in thin film alkali antimonide photocathodes from optical interference in the cathode-substrate multilayer. Modulations in the spectral response are observed over a range of visible wavelengths and are shown to increase the QE by more than a factor of two at specific wavelengths. We present a model describing the QE modulations based on the three step photoemission process incorporating cases of both constant density of states and density functional theory-derived density of states and show that the calculated results are in good agreement with the measurements. Model predictions demonstrate that QE can be enhanced by more than a factor of 5 by optimization of cathode and substrate layer thicknesses. Additionally, these calculations reveal that optical interference can yield higher quantum efficiencies in thin films compared to thick, optically dense films. We model the QE vs excitation wavelength of multiple alkali antimonide compounds at different thicknesses. We then discuss the advantages of this interference effect for electron accelerators.
A novel binary compound within the Ba–Sb phase diagram, Ba5Sb8, was synthesized by combining elements with an excess of Sb in an alumina crucible. Structural elucidation was performed using single-crystal X-ray diffraction. This compound crystallizes in the orthorhombic space group Fdd2 with unit cell parameters of a = 15.6568(13) Å, b = 35.240(3) Å, c = 6.8189(6) Å, adopting its own structure type. The most distinctive features of the structure are the eight-membered [Sb8]10− polyanionic fragments which have no known precedents among antimonides. They are separated by five Ba2+ cations, which afford the charge balance and enable adherence to the Zintl–Klemm formalism. Ba5Sb8 is the highest known member of the homologous series within the family of barium antimonides BanSb2n−2 (n ≥ 2), all of which boast anionic substructures with oligomeric moieties of pnictogen atoms with varied lengths and topologies. Electronic structure calculations indicate an indirect narrow bandgap of ca. 0.45 eV, which corroborates the valence-precise chemical bonding in Ba5Sb8.
The performance of x-ray free electron lasers and ultrafast electron diffraction experiments is largely dependent on the brightness of electron sources from photoinjectors. Here, the maximum brightness from photoinjectors at a particular accelerating gradient is limited by the mean transverse energy (MTE) of electrons emitted from photocathodes. For high quantum efficiency (QE) cathodes like alkali-antimonide thin films, which are essential to mitigate the effects of non-linear photoemission on MTE, the smallest possible MTE and, hence, the highest possible brightness are limited by the nanoscale surface roughness and chemical inhomogeneity. In this work, we show that high QE Cs 3 Sb films grown on lattice-matched strontium titanate (STO) substrates have a factor of 4 smoother, chemically uniform surfaces compared to those traditionally grown on disordered Si surfaces. We perform simulations to calculate roughness induced MTE based on measured topographical and surface-potential variations on the Cs 3 Sb films grown on STO and show that these variations are small enough to have no consequential impact on the MTE and, hence, the brightness.
In this study, we present results of our recent work of epitaxially-grown aluminum (epi-Al) on antimonide heterostructures, where the epi-Al thin film is grown at either room temperature or below zero °C. A sharp superconducting transition at T ∼ 1.3 K is observed in these epi-Al films. We further show that supercurrent states are realized in Josephson junctions fabricated in the epi-Al/antimonide heterostructures with mobility μ ∼ 1.0 × 10 6 cm 2 /Vs. These results clearly demonstrate we have achieved growing high-quality epi-Al/antimonide heterostructures, a promising platform for the exploration of Josephson junction effects for quantum information science and microelectronics applications.
The mean transverse energy (MTE) of electrons emitted from cathodes is a critical parameter that determines the brightness of electron beams for applications, such as x-ray free electron lasers, particle colliders, and ultrafast electron scattering experiments. Achieving a MTE close to the thermal limit is a key step toward realizing the full potential of electron sources in these applications. Cesium antimonide (Cs 3 Sb) is a technologically important material with a long history of use in photon detection and electron sources. The smallest MTE of electrons photoemitted from Cs 3 Sb has always been appreciably greater than the thermal limit and was attributed to surface non-uniformities. In this work, we present comprehensive measurements of the photoemission electron energy spectra (PEES), quantum efficiency, and MTE from Cs 3 Sb in a wide photoexcitation energy range from 1.5 to 2.3 eV. Our PEES measurements demonstrate a notably low photoemission threshold of around 1.5 eV, which is in contrast with the previously perceived threshold of 1.8–2.0 eV. Moreover, we show that the MTE at this threshold of 1.5 eV nearly converges to the thermal limit at 300 K. At 1.8 eV, the MTE measured is 40 meV, which is comparable to the previously reported value. Here, we conclude that this MTE value at 1.8 eV photon energy is not due to surface roughness effects as previously believed, but is a direct consequence of the excess energy.
Bismuth antimonide (Bi 1−x Sb x ) has emerged as a highly promising material for quantum applications due to its complex band structure. In this study, spherical Bi 1−x Sb x quantum dots (QDs), with a diameter of around 8 ± 2 nm, were successfully synthesized by pulsed laser ablation in liquids. The energy bandgap was determined at 2.02 ± 0.27 eV, which is significantly higher than the bulk value (∼0.025 eV). The strong confinement nature of the dots was confirmed by the Raman peak shifts. The chemical composition of the Bi 1−x Sb x QDs was measured to be around 77 ± 2 at. % of Bi and 23 ± 2 at. % of Sb. The colloid containing the Bi 1−x Sb x QDs was classified as highly stable, displaying a zeta potential of −38 ± 18 mV. Finally, the Bi 1−x Sb x QDs exhibited an electron spin resonance (ESR) signal at room temperature and at cryogenic temperature (4.2 K); consequently, revealing the presence of paramagnetic states.
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.
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