Molecular beam epitaxy growth of superconducting tantalum germanide
Patrick James Strohbeen, Tathagata Banerjee, Aurelia M. Brook, Ido Levy, Wendy L. Sarney, Jechiel van Dijk, Hayden Orth, Melissa Mikalsen, Valla Fatemi, Javad Shabani
Developing alternative material platforms for use in superconductor–semiconductor hybrid structures is desirable due to limitations caused by intrinsic microwave losses present in commonly used III/V material systems. With the recent reports on tantalum superconducting qubits that show improvements over the Nb and Al counterparts, exploring Ta the superconductor in hybrid material systems is promising. Here, we study the growth of Ta on semiconducting Ge (001) substrates grown via molecular beam epitaxy. We show that at a growth temperature of 400 °C, the Ta diffuses into the Ge matrix in a self-limiting nature resulting in smooth and abrupt surfaces and interfaces with roughness on the order of 3–7 Å as measured by atomic force microscopy and x-ray reflectivity. The films are found to be a mixture of Ta5Ge3 and TaGe2 binary alloys and form a native oxide that seems to form a sharp interface with the underlying film. These films are superconducting with a TC∼1.8−2 K and HC⊥∼1.88 T, HC∥∼5.1 T. These results show this tantalum germanide film to be promising for future superconducting quantum information platforms.
Developing alternative material platforms for use in superconductor–semiconductor hybrid structures is desirable due to limitations caused by intrinsic microwave losses present in commonly used III/V material systems. With the recent reports on tantalum superconducting qubits that show improvements over the Nb and Al counterparts, exploring Ta the superconductor in hybrid material systems is promising. Here, we study the growth of Ta on semiconducting Ge (001) substrates grown via molecular beam epitaxy. We show that at a growth temperature of 400 °C, the Ta diffuses into the Ge matrix in a self-limiting nature resulting in smooth and abrupt surfaces and interfaces with roughness on the order of 3–7 Å as measured by atomic force microscopy and x-ray reflectivity. The films are found to be a mixture of Ta5Ge3 and TaGe2 binary alloys and form a native oxide that seems to form a sharp interface with the underlying film. These films are superconducting with a TC∼1.8−2 K and HC⊥∼1.88 T, HC∥∼5.1 T. These results show this tantalum germanide film to be promising for future superconducting quantum information platforms.
Superconducting qubits are among the most advanced platforms for quantum information, offering potential scalability and compatibility with standard device fabrication techniques [1-5]. Among the materials investigated for superconducting qubits, Tantalum (Ta) has emerged as a compelling candidate due to its self-terminating stoichiometric surface oxide and chemical resistance to harsh post-fabrication processes. Efforts to mitigate surface loss by treating the surface oxides and utilizing high-resistivity silicon substrates have led to Ta-based qubits with lifetime and coherence times exceeding 1 ms [3]. Guided by these successes in reducing dielectric loss in Ta-based devices, we are interested in exploring material engineering approaches that enhance the superconducting gap. Alloying Ta with another element to enhance the superconducting performance expands the range of viable material candidates available to tackle different loss channels in superconducting circuits [1]. Recently, we explore superconducting gap engineering in Ta-based devices as a powerful strategy for expanding the range of suitable host materials. By alloying 20 at.% hafnium (Hf) into Ta thin films, we achieve a superconducting transition temperature (Tc) of 6.09 K as observed in direct current (DC) transport measurements, reflecting an increase in the superconducting gap. Here we demonstrate an approach for controlling varying deposition conditions to control film orientation and transport properties of Ta and Ta-Hf alloy thin films. We investigate the microstructure and composition distribution of the thin films by using high-resolution scanning transmission electron microscopy (STEM) with super-X EDS system (no serious beam damage issue [6-8]). Our structural analysis using TEM diffraction and STEM verifies the BCC structure across all the films (Figure 1), and direct current (DC) transport measurements reveal a 40% enhancement in Tc relative to undoped Ta (Tc=4.3 K). We monitored oxide growth over an 18-day period following film deposition to better understand how Hf incorporation influences surface oxides. In both Ta and Hf spectra, the fraction of fully oxidized (Ta2O5 and HfO2) states gradually increased during the 18-day exposure, indicating progressive surface oxidation. To estimate the surface oxide thickness, we use cross-sectional TEM/EDS mapping (Figure 1c). The analysis reveals that the oxide thickness for the 1 ks Ta-Hf alloy film is approximately 3 nm in thickness, comparable to the 3 nm oxide observed on native Ta [2]. For the 2 ks Ta-Hf film, the oxide thickness increases slightly to about 4 nm (Figure 1). The measured surface loss tangent of the Ta-Hf alloy remains comparable to that of native Ta. This result suggests that the surface oxide of the Ta-Hf alloy, which contains a measurable fraction of HfOx, does not introduce additional dielectric loss. By engineering the alloy composition and film deposition, this study achieves both improved superconducting properties and compatibility with fabrication processes. These findings show that material doping and alloying can strategically expand the suite of viable materials for superconducting quantum devices. This approach provides a pathway for tailoring material properties to support the next generation of quantum technologies and offers broad relevance to researchers in materials science, quantum information, and device engineering [9]. STEM images on cross sections of 1 ks (a) and 2 ks (b) Ta-Hf thin films, both films were sputtered at 750 ◦C. (c) Cross-sectional EDS elemental mapping on Ta-Hf. Cross-sectional EDS mapping Ta (blue) and Hf (orange) confirmed a uniform Ta-Hf alloy with the Ta to Hf atomic ratios for the bulk to be (83% : 17%). The oxygen (red) map reveals a surface oxide layer with the estimated surface oxide thickness of around 4 nm. The 1 ks Ta-Hf film exhibits an oxide thickness of approximately 3 nm, similar to that of native Ta. The EDS resolution limit is 0.5 atomic percent.
Motivated by recent advancements highlighting Ta as a promising material in low-loss superconducting circuits and showing long coherence times in superconducting qubits, we have explored the effect of cryogenic temperatures on the growth of Ta and its integration in superconducting circuits. Cryogenic growth of Ta using a low-temperature molecular beam epitaxy (MBE) system is found to stabilize single-phase $\ensuremath{\alpha}$-Ta on several different substrates, which include Al2O3(0001), Si(001), Si(111), SiNx, and GaAs(001). The substrates are actively cooled down to cryogenic temperatures and remain 20 K during the Ta deposition. X-ray $\ensuremath{\theta}$-$2\ensuremath{\theta}$ diffraction (XRD) after warming to room temperature indicates the formation of polycrystalline $\ensuremath{\alpha}$-Ta. The 50-nm $\ensuremath{\alpha}$-Ta films grown on Al2O3(0001) at a substrate manipulator temperature of 7 K have a room temperature resistivity (${\ensuremath{\rho}}_{300\phantom{\rule{0.1em}{0ex}}\mathrm{K}}$) of $13.4\phantom{\rule{0.1em}{0ex}}\text{\ensuremath{\mu}}\mathrm{\ensuremath{\Omega}}\phantom{\rule{0.2em}{0ex}}\mathrm{cm}$, a residual resistivity ratio (RRR) of 17.3 and a superconducting transition temperature (TC) of 4.14 K, which are comparable to bulk values. In addition, atomic force microscopy (AFM) indicates that the film grown at 7 K with an rms roughness of 0.45 nm was significantly smoother than the one grown at room temperature. Similar properties are found for films grown on other substrates. Results for films grown at higher substrate manipulator temperatures show higher ${\ensuremath{\rho}}_{300\phantom{\rule{0.1em}{0ex}}\mathrm{K}}$, lower RRR and Tc, and increased $\ensuremath{\beta}$-Ta content. Coplanar waveguide resonators with a gap width of $3\phantom{\rule{0.1em}{0ex}}\text{\ensuremath{\mu}}\mathrm{m}$ fabricated from cryogenically grown Ta on Si(111) and Al2O3(0001) show low-power Qi of 1.9 million and 0.7 million, respectively, indicating polycrystalline $\ensuremath{\alpha}$-Ta films may be promising for superconducting qubit applications even though they are not fully epitaxial.
The performance and coherence of superconducting quantum systems are fundamentally tied to the quality of the materials from which they are built. In superconducting transmon qubits, many loss mechanisms and sources of decoherence originate from material imperfections or unwanted oxide formation. Likewise, semiconductor–superconductor hybrid systems depend on high-quality interfaces to ensure strong coupling between electronic states in the two materials. In such hybrid devices, the accessible operating regime is often dictated by the intrinsic material properties of either the semiconductor or the superconductor. Advancing quantum device performance therefore requires exploring new material systems and optimizing their physical characteristics. In this thesis, we present the development of several superconducting material platforms for quantum technologies, including superconducting qubits, single-photon detectors, and semiconductor superconductor hybrid devices. We focus on the growth and characterization of superconducting films and heterostructures, and we establish clear connections between their material properties and the resulting device performance. First, we will present a novel semiconductor-superconductor hybrid material based on in-situ deposited epitaxial layers of Nb and Al on a shallow InAs quantum well. In this structure, the Al interlayer provides an epitaxial connection between an in-situ magnetron sputtered Nb or NbTi thin film and a shallow InAs two dimensional electron gas. This metal-to-metal epitaxy is achieved by optimization of the material stack and results in an induced superconducting gap of approximately 1 meV, determined from transport measurements of superconductor semiconductor Josephson junctions. This induced gap is approximately five times larger than the values reported for Al-based hybrid materials and indicates the formation of highly-transparent interfaces that are required in high-quality hybrid material platforms. Then, we discuss a different approach in the next chapter where we develop a hybrid material based on a molecular beam epitaxy grown InAsSb surface quantum well with an in-situ deposited Nb layer directly on top of the quantum well. Relative to conventional Al-InAs based systems, the InAsSb surface quantum well offers a lower effective mass and stronger spin-orbit interaction, while the Nb layer has a higher critical temperature and a larger critical magnetic field. The in-situ deposition of the Nb layer directly on top of the quantum well results in a high-quality interface that enables strong coupling to the InAsSb quantum well. Transport measurements on Josephson junctions reveal an induced superconducting gap of 1.3 meV and a critical current density of 3.75 × 10³A/cm². Furthermore, a planar asymmetric SQUID is realized, exhibiting gate-tunable superimposed oscillations originating from both the individual Josephson junction and the full SQUID loop. The large induced superconducting gap combined with strong spin-orbit interaction position this material as an attractive platform for experiments exploring gate-tunable superconductivity and topological superconducting devices. In the next chapter, we will focus on establishing a link between Nb film crystal properties and their performance in superconducting circuits. In this study, we investigate the microwave properties of niobium resonators with different crystalline properties and related surface topographies. We analyze a series of magnetron sputtered films in which the Nb crystal orientation and surface topography are changed by varying the substrate temperatures between room temperature and 975 K. The lowest-loss resonators that we measure have quality factors of over 10⁶ at single-photon powers, among the best ever recorded using the Nb on sapphire platform. We observe the highest quality factors in films grown at an intermediate temperature regime of the growth series (550 K) where the films display both preferential ordering of the crystal domains and low surface roughness. Furthermore, we analyze the temperature-dependent behavior of our resonators to learn about how the quasi-particle density in the Nb film is affected by the niobium crystal structure and the presence of grain boundaries. Then, we explore yet a different material platform by attempting to realize onchip NbTiN single photon detectors on LiNbO₃, an emerging photonic platform with high potential for scalable quantum information processing. We use DC reactive magnetron sputtering to grow high-quality NbTiN thin films and investigate the impact of substrate temperature during NbTiN growth. We achieve four nm thick superconducting films with a critical temperature (𝑇𝑐) of 12.3 K grown at a substrate temperature of 825 K. We demonstrate that the increased substrate temperature reduces the oxygen concentration in our films and improves the overall stoichiometry. In addition, we integrate these films with the LiNbO3 platform and investigate the obtained interface quality. Finally, we fabricate superconducting nanowire single photon detectors from the NbTiN film on LiNbO₃ and characterize the detector performance. Lastly, we report a gate-tunable Josephson diode effect in hybrid nanowire junctions consisting of a spin-orbit-coupled semiconductor core coated with epitaxial ferromagnetic insulator and superconductor shells. The wires display a hysteretic superconducting window as a function of axial magnetic field. In the superconducting regime, the devices exhibit nonreciprocal current transport, with the diode efficiency showing a strong dependence on back-gate voltage. The effect persists in a remanent magnetization state following a controlled demagnetization procedure, establishing zero-field operation. The combination of results presented in this thesis stress the importance of a material-focused approach in advancing the performance of quantum hardware. The novel hybrid material platforms developed in this thesis expand the operating regime of devices, which could enable future experiments involving gate-tunable superconductivity or topological properties. Similarly, we demonstrate that optimizing superconductor crystal structure benefits quantum devices, such as single-photon detectors and superconducting resonators.
Abstract Building usefully coherent superconducting quantum processors depends on reducing losses in their constituent materials.1 Tantalum, like niobium, has proven utility as the primary superconducting layer within highly coherent qubits.2,3 But, unlike Nb, high temperatures are typically used to stabilize the desirable body-centered-cubic phase, α-Ta, during thin film deposition. It has long been known that a thin Nb layer permits the room-temperature nucleation of α-Ta,4-6 although neither an epitaxial process nor few-photon microwave loss measurements have been reported for Nb-nucleated Ta films prior to this study. We compare resonators patterned from Ta films grown at high temperature (500 °C) and films nucleated at room temperature, in order to understand the impact of crystalline order on quantum coherence. In both cases, films grew with Al2O3 (001) || Ta (110) indicating that the epitaxial orientation is independent of temperature and is preserved across the Nb/Ta interface. We use conventional low-power spectroscopy to measure two level system (TLS) loss, as well as an electric-field bias technique to measure the effective dipole moments of TLS in the surfaces of resonators. In our measurements, Nb-nucleated Ta resonators had greater loss tangent (1.5 ± 0.1 × 10-5) than nonnucleated (5 ± 1 × 10-6) in approximate proportion to defect densities as characterized by X-ray diffraction (0.27 ° vs 0.18 ° [110] reflection width) and electron microscopy (30 nm vs 70 nm domain size). The dependence of the loss tangent on domain size indicates that the development of more ordered Ta films is likely to lead to improvements in qubit coherence times.1,7 Moreover, lowtemperature α-Ta epitaxy may enable the growth of new, microstate-free heterostructures which would not withstand high temperature processing.8
Polycrystalline α-tantalum (110) films deposited on the c-plane sapphire substrate by sputtering are used in superconducting qubits nowadays. However, these films always occasionally form other structures, such as α-tantalum (111) grains and β-tantalum grains. To improve the film quality, we investigate the growth of α-tantalum (110) films on the a-plane sapphire substrate under varying conditions by molecular beam epitaxy technology. The optimized α-tantalum (110) film is a single crystal, with a smooth surface and atomically flat metal–substrate interface. The film with thickness of 30 nm shows a Tc of 4.12 K and a high residual resistance ratio of 9.53. The quarter wavelength coplanar waveguide resonators fabricated with the 150 nm optimized α-tantalum (110) film exhibit intrinsic quality factor of over one million under single photon excitation at millikelvin temperature.
Quantum coherence in superconducting circuits has increased steadily over the last decades as a result of a growing understanding of the various loss mechanisms. Recently, tantalum (Ta) emerged as a promising material to address microscopic sources of loss found on niobium (Nb) or aluminum (Al) surfaces. However, the effects of film and interface microstructure on low-temperature microwave loss are still not well understood. Here we present a systematic study of the structural and electrical properties of Ta and Nb films sputtered on c-plane sapphire at varying growth temperatures. As growth temperature is increased, our results show that the onset of epitaxial growth of alpha-phase Ta correlates with lower Ta surface roughness, higher critical temperature, and higher residual resistivity ratio, but surprisingly also correlates with a significant increase in loss at microwave frequency. Notably, this high level of loss is not observed in Nb films prepared in the same way and having very similar structure. By experimentally controlling the surface on which the Ta film is nucleated, we determine that the source of loss is only present in samples having an epitaxial Ta/sapphire interface and show that it is apparently mitigated by either growing a thin, epitaxial Nb inter-layer between the Ta film and the substrate or by intentionally treating, and effectively damaging, the sapphire surface with an in-situ argon plasma before Ta growth. In addition to elucidating this interfacial microwave loss, this work provides adequate process details to aid reproducible growth of low-loss Ta films across fabrication facilities.