Oxide electronics

Abstract:

The [Zn_1-xNi_x(HF₂)(pyz)₂]SbF₆ (x = 0.2; pyz = pyrazine) solid solution exhibits a zero-field splitting (D) that is 22% larger [D = 16.2(2) K (11.3(2) cm^-1)] than that observed in the x = 1 material [D = 13.3(1) K (9.2(1) cm^-1)]. The substantial change in D is accomplished by an anisotropic lattice expansion in the MN₄ (M = Zn or Ni) plane, wherein the increased concentration of isotropic Zn(II) ions induces a nonlinear variation in M-F and M-N bond lengths. In this, we exploit the relative donor atom hardness, where M-F and M-N form strong ionic and weak coordinate covalent bonds, respectively, the latter being more sensitive to substitution of Ni by the slightly larger Zn(II) ion. In this way, we are able to tune the single-ion anisotropy of a magnetic lattice site by Zn-substitution on nearby sites. This effect has possible applications in the field of single-ion magnets and the design of other molecule-based magnetic systems.

Abstract:

Antiferromagnetic insulators are a ubiquitous class of magnetic materials, holding the promise of low-dissipation spin-based computing devices that can display ultra-fast switching and are robust against stray fields. However, their imperviousness to magnetic fields also makes them difficult to control in a reversible and scalable manner. Here we demonstrate a novel proof-of-principle ionic approach to control the spin reorientation (Morin) transition reversibly in the common antiferromagnetic insulator α-Fe₂O₃ (haematite) - now an emerging spintronic material that hosts topological antiferromagnetic spin-textures and long magnon-diffusion lengths. We use a low-temperature catalytic-spillover process involving the post-growth incorporation or removal of hydrogen from α-Fe₂O₃ thin films. Hydrogenation drives pronounced changes in its magnetic anisotropy, Néel vector orientation and canted magnetism via electron injection and local distortions. We explain these effects with a detailed magnetic anisotropy model and first-principles calculations. Tailoring our work for future applications, we demonstrate reversible control of the room-temperature spin-state by doping/expelling hydrogen in Rh-substituted α-Fe₂O₃.

Abstract:

We present a crystallographic and optoelectronic study of the double perovskite Cs2AgBi1–xInxBr6. From structural characterization we determine that the indium cation shrinks the lattice and shifts the cubic-to-tetragonal phase transition point to lower temperatures. The absorption onset is shifted to shorter wavelengths upon increasing the indium content, leading to wider band gaps, which we rationalize through first-principles band structure calculations. Despite the unfavorable band gap shift, we observe an enhancement in the steady-state photoluminescence intensity, and n-i-p photovoltaic devices present short-circuit current greater than that of neat Cs2AgBiBr6 devices. In order to evaluate the prospects of this material as a solar absorber, we combine accurate absorption measurements with thermodynamic modeling and identify the fundamental limitations of this system. Provided radiative efficiency can be increased and the choice of charge extraction layers are specifically improved, this material could prove to be a useful wide band gap solar absorber.

Abstract:

In the quest for post-CMOS (complementary metal–oxide–semiconductor) technologies, driven by the need for improved efficiency and performance, topologically protected ferromagnetic ‘whirls’ such as skyrmions1,2,3,4,5,6,7,8 and their anti-particles have shown great promise as solitonic information carriers in racetrack memory-in-logic or neuromorphic devices1,9,10,11. However, the presence of dipolar fields in ferromagnets, which restricts the formation of ultrasmall topological textures3,6,8,9,12, and the deleterious skyrmion Hall effect, when skyrmions are driven by spin torques9,10,12, have thus far inhibited their practical implementation. Antiferromagnetic analogues, which are predicted to demonstrate relativistic dynamics, fast deflection-free motion and size scaling, have recently become the subject of intense focus9,13,14,15,16,17,18,19, but they have yet to be experimentally demonstrated in natural antiferromagnetic systems. Here we realize a family of topological antiferromagnetic spin textures in α-Fe2O3—an Earth-abundant oxide insulator—capped with a platinum overlayer. By exploiting a first-order analogue of the Kibble–Zurek mechanism20,21, we stabilize exotic merons and antimerons (half-skyrmions)8 and their pairs (bimerons)16,22, which can be erased by magnetic fields and regenerated by temperature cycling. These structures have characteristic sizes of the order of 100 nanometres and can be chemically controlled via precise tuning of the exchange and anisotropy, with pathways through which further scaling may be achieved. Driven by current-based spin torques from the heavy-metal overlayer, some of these antiferromagnetic textures could emerge as prime candidates for low-energy antiferromagnetic spintronics at room temperature1,9,10,11,23.

Abstract:

Mixed-halide perovskites offer bandgap tunability essential for multijunction solar cells; however, a detrimental halide segregation under light is often observed. Here we combine simultaneous in situ photoluminescence and X-ray diffraction measurements to demonstrate clear differences in compositional and optoelectronic changes associated with halide segregation in MAPb(Br_0.5I_0.5)₃ and FA_0.83Cs_0.17Pb(Br_0.4I_0.6)₃ films. We report evidence for low-barrier ionic pathways in MAPb(Br_0.5I_0.5)₃, which allow for the rearrangement of halide ions in localized volumes of perovskite without significant compositional changes to the bulk material. In contrast, FA_0.83Cs_0.17Pb(Br_0.4I_0.6)₃ lacks such low-barrier ionic pathways and is, consequently, more stable against halide segregation. However, under prolonged illumination, it exhibits a considerable ionic rearrangement throughout the bulk material, which may be triggered by an initial demixing of A-site cations, altering the composition of the bulk perovskite and reducing its stability against halide segregation. Our work elucidates links between composition, ionic pathways, and halide segregation, and it facilitates the future engineering of phase-stable mixed-halide perovskites.