We report the synthesis and transfer of epitaxial germanane (GeH) onto arbitrary substrates by electrochemical delamination and investigate its optoelectronic properties. GeH films with thickness ranging from 1 to 600 nm (2-1000 layers) and areas up to ∼1 cm 2 have been reliably transferred and characterized by photoluminescence, x-ray diffraction, and energy-dispersive x-ray spectroscopy. Wavelength dependent photoconductivity measurements on few-layer GeH exhibit an absorption edge and provide a sensitive characterization tool for ultrathin germanane materials. The transfer process also enables the possibility of integrating germanane into vertically stacked heterostructures.

We observe the magnetic proximity effect (MPE) in Pt/CoFe 2 O 4 bilayers grown by molecular beam epitaxy (MBE). This is revealed through angle-dependent magnetoresistance measurements at 5 K, which isolate the contributions of induced ferromagnetism (i.e. anisotropic magnetoresistance) and spin Hall effect (i.e. spin Hall magnetoresistance) in the Pt layer. The observation of induced ferromagnetism in Pt via AMR is further supported by density functional theory calculations and various control measurements including insertion of a Cu spacer layer to suppress the induced ferromagnetism. In addition, anomalousHall effect measurements show an out-of-plane magnetic hysteresis loop of the induced ferromagnetic phase with larger coercivity and larger remanence than the bulk CoFe 2 O 4 . By demonstrating MPE in Pt/CoFe 2 O 4 , these results establish the spinel ferrite family as a promising material for MPE and spin manipulation via proximity exchange fields.* equal contributions **email: kawakami.15@osu.edu 2 Spin manipulation inside a nonmagnetic (NM) material using internal effective fields (spin orbit or exchange) is a very promising avenue toward the realization of next generation spintronic devices (spin transistors, magnetic gates, etc.) [1,2]. In particular, magnetic proximity effect (MPE) at the interface of a NM spin channel and a ferromagnetic insulator (FMI) is of great importance for generating exchange fields and induced ferromagnetism in the NM layer. Recently, spin manipulation by MPE has been realized in experiments that modulate spin currents in graphene on YIG (yttrium iron garnet) [3,4]. In addition, proximity exchange fields induced by FMI have been observed for graphene and monolayer transition transition metal dichalcogenides [5,6].Among FMIs, members of the spinel ferrite family (MFe 2 O 4 , with M=Co, Ni, etc.) are attractive because their magnetic properties can be tuned by alloy composition [7,8] as well as epitaxial strain [9][10][11]. In particular, CoFe 2 O 4 (CFO) is a hard ferrimagnetic insulator which exhibits high Curie temperature (728 K), spin-filtering properties [12][13][14], magneto-electric switching [15], and is readily integrated with practical spintronic materials (MgO, Fe, Cr). Unfortunately, all previous experiments have failed to observe MPE using CFO. To test for MPE in NM/FMI systems, Pt is widely used as the NM material due its closeness to fulfilling the Stoner criteria and thus allowing it to become ferromagnetically ordered at the interface with the FMI. Initial studies of Pt/CFO grown by pulsed laser deposition (PLD) utilized magnetotransport measurements and observed no MPE in the Pt layer [16]. Subsequent transport and element-specific magnetization measurements by x-ray magnetic circular dichroism (XMCD) also found no evidence for induced ferromagnetism in the Pt layer [17][18][19][20] contributing to a growing consensus that CFO cannot be used to obtain MPE. However, because the length scale of exchange interactions is on the order of angstroms, it should...

Two-dimensional crystals are an important class of materials for novel physics, chemistry, and engineering. Germanane (GeH), the germanium-based analogue of graphane (CH), is of particular interest due to its direct band gap and spin-orbit coupling. Here, we report the successful co-deposition growth of CaGe 2 films on Ge(111) substrates by molecular beam epitaxy (MBE) and their subsequent conversion to germanane by immersion in hydrochloric acid. We find that the growth of CaGe 2 occurs within an adsorption-limited growth regime, which ensures stoichiometry of the film. We utilize in situ reflection high energy electron diffraction (RHEED) to explore the growth temperature window and find the best RHEED patterns at 750 °C. Finally, the CaGe 2 films are immersed in hydrochloric acid to convert the films to germanane. Auger electron spectroscopy of the resulting film indicates the removal of Ca and RHEED patterns indicate a single-crystal film with in-plane orientation dictated by the underlying Ge(111) substrate. X-ray diffraction and Raman spectroscopy indicate that the resulting films are indeed germanane. Ex situ atomic force microscopy (AFM) shows that the grain size of the germanane is on the order of a few micrometers, being primarily limited by terraces induced by the miscut of the Ge substrate.Thus, optimization of the substrate could lead to the long-term goal of large area germanane films.2

The ability to optically manipulate spin states has potential to enable ultrafast magnetization switching at rates that are several orders faster than magnetic precession. However, controlling these processes requires understanding of the site-specific charge transfer and spin dynamics during optical excitation and subsequent hot carrier relaxation. Nickel ferrite (NFO) is a ferrimagnetic semiconductor with potential for ultrafast switching. Because of the partial degree of inversion, 12 possible charge transfer excitations exist in NFO. Using extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy to measure the Fe M-edge, Ni M-edge, and O L-edge spectra with femtosecond time resolution reveals that 400 nm light excites an electron transfer from O 2p valence band states to Fe 3d conduction band states. Kinetic analysis shows that this charge transfer state undergoes fast electron and hole polaron formation, where electrons localize to O h Fe centers and holes localize to O h Ni centers. Hole polaron formation increases the crystal field splitting around Ni which drives a spin-state transition leading to a low-spin O h Ni3+ final state within 0.326 ± 0.14 ps. This study reveals the mechanism of ultrafast optical spin switching in NFO and highlights the capability of XUV spectroscopy to elucidate these dynamics with unprecedented temporal and site-specific resolution.

We investigate the initial growth modes and the role of interfacial

Transition metal complexes capable of photo-induced spin crossover have been widely investigated because of their potential to enable ultrafast optical control of information processing. However, any real application of photo-switchable molecules requires that spin crossover be paired with additional functionality such as long-range magnetic order. Important advances combining these functions are notably reported for a number of bimetallic Prussian Blue analogues; however, to date PBA-based magnetic photo-switches can only operate below 150 K due to loss of magnetic order. In contrast, cobalt ferrite is a ferrimagnetic semiconductor with a Curie temperature of 790 K and extremely favorable magnetic properties by comparison to state-of-the-art PBAs. The mixed valence electronic structure of cobalt ferrite is reminiscent of cobalt-iron PBA, which is a well-known photo-switch. To investigate the potential for photo-switching in this material, we employ transient XUV spectroscopy to probe charge and spin dynamics with element-speci fic resolution on the femtosecond time scale. Results show that 400 nm light excites a metal-to-metal charge transfer transition, which drives the crossover of high-spin Co2+ to low-spin Co3+ with a time constant of 405 ± 29 fs and an internal quantum efficiency of unity. This result establishes the existence of efficient photo-switching in a new class of robust ferrimagnetic spinel ferrites. File list (2) download file view on ChemRxiv CFO_Main Mauscript.pdf (0.98 MiB) download file view on ChemRxiv CFO_Supplementary_Information.pdf (840.14 KiB)

Ultrathin films of Na 3 Bi on insulating substrates are desired for opening a bulk band gap and generating the quantum spin Hall effect from a topological Dirac semimetal, though continuous films in the few nanometer regime have been difficult to realize. Here, we utilize alternating layer molecular beam epitaxy (MBE) to achieve uniform and continuous single crystal films of Na 3 Bi(0001) on insulating Al 2 O 3 (0001) substrates and demonstrate electrical transport on films with 3.8 nm thickness (4 unit cells). The high material quality is confirmed through in situ reflection high-energy electron diffraction (RHEED), scanning tunneling microscopy (STM), xray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS). In addition, these films are employed as seed layers for subsequent growth by codeposition, leading to atomic layer-bylayer growth as indicated by RHEED intensity oscillations. These material advances facilitate the pursuit of quantum phenomena in thin films of Dirac semimetals.

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