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We report a two-step film-growth process using suboxide molecular-beam epitaxy (S-MBE) that produces Si-doped α-Ga2O3 with record transport properties. The method involves growing a relaxed α-(AlxGa1−x)2O3 buffer layer on m-plane sapphire at a relatively high substrate temperature (Tsub), ∼750 °C, followed by an Si-doped α-Ga2O3 overlayer grown at lower Tsub, ∼500 °C. The high Tsub allows the ∼3.6% lattice-mismatched α-(AlxGa1−x)2O3 buffer with x = 0.08 ± 0.02 to remain epitaxial and phase pure during relaxation to form a pseudosubstrate for the overgrowth of α-Ga2O3. The optimal conditions for the subsequent growth of Si-doped α-Ga2O3 by S-MBE are 425 °C ≤ Tsub ≤ 500 °C and P80% O3 = 5 × 10−6 Torr. Si-doped α-Ga2O3 films grown with this method at Tsub > 550 °C are always insulating. Secondary-ion mass spectrometry confirms that both the insulating and conductive films have uniform silicon incorporation. In conductive films with 1019 ≤ NSi ≤ 1020 cm−3, the incorporated silicon is ∼100% electrically active. At NSi ≤ 1019 cm−3, the carrier concentration (n) plummets. A maximum Hall mobility (μ) = 90 cm2V·s at room-temperature is measured in a film with n = 2.9 × 1019 cm−3 and a maximum conductivity (σ) = 650 S/cm at room-temperature in a film with n = 4.8 × 1019 cm−3. A threading dislocation density of (5.6 ± 0.6) × 1010 cm−2 is revealed by scanning transmission electron microscopy, showing that there is still enormous room to improve the electrical properties of doped α-Ga2O3 thin films. 

Abstract Bridging functionalities in periodic mesoporous organosilicas (PMOs) enable new functionalities for a wide range of applications. Bridge cleavage is frequently observed during anneals required to form porous structures, yet the mechanism of these bridge cleavages has not been completely resolved. Here, these chemical transformations and their kinetic pathways on sub‐millisecond timescales induced by laser heating are revealed. By varying anneal times and temperatures, the transformation dynamics of bridge cleavage and structural transformations and their activation energies are determined. The structural relaxation time for individual reactions and their effective local heating time are determined and compared, and the results directly demonstrate the manipulation of different molecules through kinetic control of the sequence of reactions. By isolating and understanding the earliest stage of structural transformations, this study identifies the kinetic principles for new synthesis and post‐processing routes to control individual molecules and reactions in PMOs and other material systems with multi‐functionalities. 

In this study, we investigate in situ etching of β-Ga2O3 in a metalorganic chemical vapor deposition system using tert-butyl chloride (TBCl). We report etching of both heteroepitaxial 2¯01-oriented and homoepitaxial (010)-oriented β-Ga2O3 films over a wide range of substrate temperatures, TBCl molar flows, and reactor pressures. We infer that the likely etchant is HCl (g), formed by the pyrolysis of TBCl in the hydrodynamic boundary layer above the substrate. The temperature dependence of the etch rate reveals two distinct regimes characterized by markedly different apparent activation energies. The extracted apparent activation energies suggest that at temperatures below ∼800 °C, the etch rate is likely limited by desorption of etch products. The relative etch rates of heteroepitaxial 2¯01 and homoepitaxial (010) β-Ga2O3 were observed to scale by the ratio of the surface energies, indicating an anisotropic etch. Relatively smooth post-etch surface morphology was achieved by tuning the etching parameters for (010) homoepitaxial films. 

Here, we report that a source of Si impurities commonly observed on (010) β-Ga2O3 is from exposure of the surface to air. Moreover, we find that a 15 min hydrofluoric acid (HF) (49%) treatment reduces the Si density by approximately 1 order of magnitude on (010) β-Ga2O3 surfaces. This reduction in Si is critical for the elimination of the often observed parasitic conducting channel, which negatively affects transport properties and lateral transistor performance. After the HF treatment, the sample must be immediately put under vacuum, for the Si fully returns within 10 min of additional air exposure. Finally, we demonstrate that performing a 30 min HF (49%) treatment on the substrate before growth has no deleterious effect on the structure or on the epitaxy surface after subsequent Ga2O3 growth. 

Preserving a contamination-free metal–semiconductor interface in β-Ga2O3 is critical to achieve consistently low resistance (< 1 Ω-mm) ohmic contacts. Here, we report a scanning transmission electron microscopy study on the variation in Ti/Au ohmic contact quality to (010) β-Ga2O3 in a conventional lift-off vs a metal-first process. We observe a thin ∼1 nm carbon barrier between the Ti and Ga2O3 in a non-conductive contact fabricated by a conventional lift-off process, which we attribute to photoresist residue, not previously detected by x-ray photoelectron spectroscopy due to the thinness and patchy coverage of the carbon layer, as well as roughness of the Ga2O3 surface. This thin carbon barrier is confirmed by electron energy loss spectroscopy and atomic force microscopy-infrared spectroscopy. We believe that the presence of the thin and patchy carbon layer leads to the highly inconsistent contact behavior in previous reports on non-alloyed contacts. Adventitious carbon is also observed in a conductive ohmic contact metal-first processing on an as-grown sample. We find that a five minute active oxygen descum is sufficient to remove this carbon on as-grown samples, further improving the ohmic behavior and reducing the contact resistance Rc to 0.06 Ω-mm. We also show that an hour long UV-ozone treatment of the Ga2O3 surface can eliminate carbon residue from the lift-off processing, resulting in a low Rc of 0.05 Ω-mm. 

Abstract Surface structures on radio-frequency (RF) superconductors are crucially important in determining their interaction with the RF field. Here we investigate the surface compositions, structural profiles, and valence distributions of oxides, carbides, and impurities on niobium (Nb) and niobium–tin (Nb₃Sn)in situunder different processing conditions. We establish the underlying mechanisms of vacuum baking and nitrogen processing in Nb and demonstrate that carbide formation induced during high-temperature baking, regardless of gas environment, determines subsequent oxide formation upon air exposure or low-temperature baking, leading to modifications of the electron population profile. Our findings support the combined contribution of surface oxides and second-phase formation to the outcome of ultra-high vacuum baking (oxygen processing) and nitrogen processing. Also, we observe that vapor-diffused Nb₃Sn contains thick metastable oxides, while electrochemically synthesized Nb₃Sn only has a thin oxide layer. Our findings reveal fundamental mechanisms of baking and processing Nb and Nb₃Sn surface structures for high-performance superconducting RF and quantum applications. 

Intermetallic Nb3Sn alloys have long been believed to form through Sn diffusion into Nb. However, our observations of significant oxygen content in Nb3Sn prompted an investigation of alternative formation mechanisms. Through experiments involving different oxide interfaces (clean HF-treated, native oxidized, and anodized), we demonstrate a thermodynamic route that fundamentally challenges the conventional Sn diffusion mechanism for Nb3Sn nucleation. Our results highlight the critical involvement of a SnOx intermediate phase. This new nucleation mechanism identifies the principles for growth optimization and new synthesis of high-quality Nb3Sn superconductors. 

Abstract Workbench-size particle accelerators, enabled by Nb₃Sn-based superconducting radio-frequency (SRF) cavities, hold the potential of driving scientific discovery by offering a widely accessible and affordable source of high-energy electrons and x-rays. Thin-film Nb₃Sn RF superconductors with high quality factors, high operation temperatures, and high-field potentials are critical for these devices. However, surface roughness, non-stoichiometry, and impurities in Nb₃Sn deposited by conventional Sn-vapor diffusion prevent them from reaching their theoretical capabilities. Here we demonstrate a seed-free electrochemical synthesis that pushes the limit of chemical and physical properties in Nb₃Sn. Utilization of electrochemical Sn pre-deposits reduces the roughness of converted Nb₃Sn by five times compared to typical vapor-diffused Nb₃Sn. Quantitative mappings using chemical and atomic probes confirm improved stoichiometry and minimized impurity concentrations in electrochemically synthesized Nb₃Sn. We have successfully applied this Nb₃Sn to the large-scale 1.3 GHz SRF cavity and demonstrated ultra-low BCS surface resistances at multiple operation temperatures, notably lower than vapor-diffused cavities. Our smooth, homogeneous, high-purity Nb₃Sn provides the route toward high efficiency and high fields for SRF applications under helium-free cryogenic operations. 

Optimizing thermal anneals of Si-implanted β-Ga2O3 is critical for low resistance contacts and selective area doping. We report the impact of annealing ambient, temperature, and time on the activation of room temperature ion-implanted Si in β-Ga2O3 at concentrations from 5 × 1018 to 1 × 1020 cm−3, demonstrating full activation (>80% activation, mobilities >70 cm2/V s) with contact resistances below 0.29 Ω mm. Homoepitaxial β-Ga2O3 films, grown by plasma-assisted molecular beam epitaxy on Fe-doped (010) substrates, were implanted at multiple energies to yield 100 nm box profiles of 5 × 1018, 5 × 1019, and 1 × 1020 cm−3. Anneals were performed in an ultra-high vacuum-compatible quartz furnace at 1 bar with well-controlled gas compositions. To maintain β-Ga2O3 stability, pO2 must be greater than 10−9 bar. Anneals up to pO2 = 1 bar achieve full activation at 5 × 1018 cm−3, while 5 × 1019 cm−3 must be annealed with pO2 ≤ 10−4 bar, and 1 × 1020 cm−3 requires pO2 < 10−6 bar. Water vapor prevents activation and must be maintained below 10−8 bar. Activation is achieved for anneal temperatures as low as 850 °C with mobility increasing with anneal temperatures up to 1050 °C, though Si diffusion has been reported above 950 °C. At 950 °C, activation is maximized between 5 and 20 min with longer times resulting in decreased carrier activation (over-annealing). This over-annealing is significant for concentrations above 5 × 1019 cm−3 and occurs rapidly at 1 × 1020 cm−3. Rutherford backscattering spectrometry (channeling) suggests that damage recovery is seeded from remnant aligned β-Ga2O3 that remains after implantation; this conclusion is also supported by scanning transmission electron microscopy showing retention of the β-phase with inclusions that resemble the γ-phase. 

Abstract Superconducting radio‐frequency (SRF) resonators are critical components for particle accelerator applications, such as free‐electron lasers, and for emerging technologies in quantum computing. Developing advanced materials and their deposition processes to produce RF superconductors that yield nΩ surface resistances is a key metric for the wider adoption of SRF technology. Here, ZrNb(CO) RF superconducting films with high critical temperatures (T_c) achieved for the first time under ambient pressure are reported. The attainment of aT_cnear the theoretical limit for this material without applied pressure is promising for its use in practical applications. A range ofT_c, likely arising from Zr doping variation, may allow a tunable superconducting coherence length that lowers the sensitivity to material defects when an ultra‐low surface resistance is required. The ZrNb(CO) films are synthesized using a low‐temperature (100 – 200 °C) electrochemical recipe combined with thermal annealing. The phase transformation as a function of annealing temperature and time is optimized by the evaporated Zr‐Nb diffusion couples. Through phase control, one avoids hexagonal Zr phases that are equilibrium‐stable but degradeT_c. X‐ray and electron diffraction combined with photoelectron spectroscopy reveal a system containing cubic β‐ZrNb mixed with rocksalt NbC and low‐dielectric‐loss ZrO₂. Proof‐of‐concept RF performance of ZrNb(CO) on an SRF sample test system is demonstrated. BCS resistance trends lower than reference Nb, while quench fields occur at approximately 35 mT. The results demonstrate the potential of ZrNb(CO) thin films for particle accelerators and other SRF applications.