Magnetic Amplification at Yb3+ "Designer Defects" in the van der Waals Ferromagnet CrI3.

The two-dimensional (2D) van der Waals ferromagnet CrI3 has been doped with the magnetic optical impurity Yb3+ to yield materials that display sharp multiline Yb3+ photoluminescence (PL) controlled by the magnetism of CrI3. Magneto-PL shows that Yb3+ magnetization is pinned to the magnetization of CrI3. An effective internal field of ∼10 T at Yb3+ is estimated, attributed to strong in-plane Yb3+-Cr3+ superexchange coupling. The anomalously low energy of Yb3+ PL in CrI3 reflects relatively high Yb3+-I- covalency, contributing to Yb3+-Cr3+ superexchange coupling. The Yb3+ PL energy and line width both reveal the effects of spontaneous zero-field CrI3 magnetic ordering within 2D layers below TC, despite the absence of net magnetization in multilayer samples. These results illustrate the use of optical impurities as "designer defects" to introduce unique functionality to 2D magnets.

Nonvolatile Memristive Effect in Few-Layer CrI3 Driven by Electrostatic Gating.

The potential of memristive devices for applications in nonvolatile memory and neuromorphic computing has sparked considerable interest, particularly in exploring memristive effects in two-dimensional (2D) magnetic materials. However, the progress in developing nonvolatile, magnetic field-free memristive devices using 2D magnets has been limited. In this work, we report an electrostatic-gating-induced nonvolatile memristive effect in CrI3-based tunnel junctions. The few-layer CrI3-based tunnel junction manifests notable hysteresis in its tunneling resistance as a function of gate voltage. We further engineered a nonvolatile memristor using the CrI3 tunneling junction with low writing power and at zero magnetic field. We show that the hysteretic transport observed is not a result of trivial effects or inherent magnetic properties of CrI3. We propose a potential association between the memristive effect and the newly predicted ferroelectricity in CrI3 via gating-induced Jahn-Teller distortion. Our work illuminates the potential of 2D magnets in developing next-generation advanced computing technologies.

One Million Percent Tunnel Magnetoresistance in a Magnetic van der Waals Heterostructure.

We report the observation of a very large negative magnetoresistance effect in a van der Waals tunnel junction incorporating a thin magnetic semiconductor, CrI3, as the active layer. At constant voltage bias, current increases by nearly one million percent upon application of a 2 T field. The effect arises from a change between antiparallel to parallel alignment of spins across the different CrI3 layers. Our results elucidate the nature of the magnetic state in ultrathin CrI3 and present new opportunities for spintronics based on two-dimensional materials.

Large Vertical Piezoelectricity in a Janus Cr2I3F3 Monolayer.

Two-dimensional (2D) materials have potential applications in nanoscale sensors and spintronic devices. Herein, motivated by experimental synthesis of a CrI3 monolayer possessing intrinsic magnetism and a Janus MoSSe monolayer with piezoelectricity, we propose a 2D Janus Cr2I3F3 monolayer as a multifunctional material exhibiting both piezoelectricity and ferromagnetism. Using density functional theory calculations, we systematically investigated the structural stability and the electronic, magnetic, and piezoelectric properties of the Janus Cr2I3F3 monolayer. We predicted that a vertical polarization of up to -0.155 × 10-10 C/m is induced in the Cr2I3F3 monolayer due to the breaking of symmetry. The origination mechanism of polarization was demonstrated in terms of a local dipole moment calculated by maximally localized Wannier functions. Meanwhile, it was found that a remarkable piezoelectric response can be produced under a uniaxial strain in the basal plane. The calculated piezoelectric coefficients of the Cr2I3F3 monolayer compare favorably with those of the frequently used bulk piezoelectric materials such as α-quartz and wurtzite AlN. Particularly, the e31 and d31 values of the Cr2I3F3 monolayer are nearly 10 times as large as that of Mo-based transition metal dichalcogenides. We also found that the magnitude of e31 mainly arises from the ionic contribution, while the electronic contribution can be nearly neglected. The considerable piezoelectric response combined with the intrinsic magnetism make the Janus Cr2I3F3 monolayer a potential candidate for novel multifunctional devices integrating both piezoelectric and spintronic applications.

Ambient-Stable Two-Dimensional CrI3 via Organic-Inorganic Encapsulation.

Two-dimensional transitional metal halides have recently attracted significant attention due to their thickness-dependent and electrostatically tunable magnetic properties. However, this class of materials is highly reactive chemically, which leads to irreversible degradation and catastrophic dissolution within seconds in ambient conditions, severely limiting subsequent characterization, processing, and applications. Here, we impart long-term ambient stability to the prototypical transition metal halide CrI3 by assembling a noncovalent organic buffer layer, perylenetetracarboxylic dianhydride (PTCDA), which templates subsequent atomic layer deposition (ALD) of alumina. X-ray photoelectron spectroscopy demonstrates the necessity of the noncovalent organic buffer layer since the CrI3 undergoes deleterious surface reactions with the ALD precursors in the absence of PTCDA. This organic-inorganic encapsulation scheme preserves the long-range magnetic ordering in CrI3 down to the monolayer limit as confirmed by magneto-optical Kerr effect measurements. Furthermore, we demonstrate field-effect transistors, photodetectors, and optothermal measurements of CrI3 thermal conductivity in ambient conditions.

Magneto-Memristive Switching in a 2D Layer Antiferromagnet.

Memristive devices whose resistance can be hysteretically switched by electric field or current are intensely pursued both for fundamental interest as well as potential applications in neuromorphic computing and phase-change memory. When the underlying material exhibits additional charge or spin order, the resistive states can be directly coupled, further allowing electrical control of the collective phases. The observation of abrupt, memristive switching of tunneling current in nanoscale junctions of ultrathin CrI3 , a natural layer antiferromagnet, is reported here. The coupling to spin order enables both tuning of the resistance hysteresis by magnetic field and electric-field switching of magnetization even in multilayer samples.