Microchemical Engineering in a 3D Ordered Channel Enhances Electrocatalysis.

The kinetics of electrode reactions including mass transfer and surface reaction is essential in electrocatalysis, as it strongly determines the apparent reaction rates, especially on nanostructured electrocatalysts. However, important challenges still remain in optimizing the kinetics of given catalysts with suitable constituents, morphology, and crystalline design to maximize the electrocatalytic performances. We propose a comprehensive kinetic model coupling mass transfer and surface reaction on the nanocatalyst-modified electrode surface to explore and shed light on the kinetic optimization in electrocatalysis. Moreover, a theory-guided microchemical engineering (MCE) strategy has been demonstrated to rationally redesign the catalysts with optimized kinetics. Experimental measurements for methanol oxidation reaction in a 3D ordered channel with tunable channel sizes confirm the calculation prediction. Under the optimized channel size, mass transfer and surface reaction in the channeled microreactor are both well regulated. This MCE strategy will bring about a significant leap forward in structured catalyst design and kinetic modulation.

Magnetotransport and magnetic properties of the layered noncollinear antiferromagnetic Cr2Se3 single crystals.

We report on the growth of high-quality stoichiometric layered Cr2Se3 single crystals with metallic and noncollinear antiferromagnetic ground state using the chemical vapor transport (CVT) method. The crystals show weak ferromagnetism in the in-plane and out-of-plane directions below the Neél temperature (T N), however, the field-cooled out-of-plane magnetization at 500 Oe and 10 K (∼0.24 µ B/f.u.) is approximately 15 times larger than that of the in-plane one, indicating strong c-axis easy uniaxial magnetic anisotropy, which is further supported by the in-plane and out-of-plane isothermal anisotropic magnetic hysteresis loops and the angular dependent magnetoresistance (MR). The latter also reveals a decrease of the coercive field of the crystal upon the tilting of the weak ferromagnetic easy axis away from the direction of the magnetic field. Further, the out-of-plane isothermal MR are negative below T N and show butterfly shapes for T < 10 K and couple with the magnetic hysteresis M(H) loop. These results may help researchers better understand the interplay between the weak ferromagnetism and the magnetotransport properties of 2D itinerant noncollinear antiferromagnetic systems.

Magnetotransport properties of square-net compounds of NbSiSb and NbGeSb single crystals.

We successfully grew single crystals of Si- and Ge-square-net compounds of NbSiSb and NbGeSb whose excellent crystalline quality are verified using single-crystal x-ray diffraction θ-2θ scans, rocking curves, scanning and transmission electron microscopies. Since these two compounds share major crystallographic similarity with the topological nodal-line semimetals of ZrSiS family, we employ density functional theory (DFT) calculations and magnetotransport measurements to demonstrate their band structures as well as the electron scattering mechanisms. DFT calculations show that the fermiology displays strong anisotropy from the crystallographic c-axis to the ab-plane and weak anisotropy within the ab plane, which is consistent with the strong anisotropic magnetotransport behaviors. Following the Kohler's scaling rule we prove that similar interband and intraband electron-phonon scattering mechanisms work in both the NbSiSb and NbGeSb compounds. The study of electronic transport mechanism in the presence of external magnetic field renders deep insight into topological behavior together with its Fermi surface, and the high similarity of crystallography and strong difference in band structures between the present single crystals and that of ZrSiS family provides the possibility to tune the band structure via element doping.

Nonvolatile Control of the Electronic Properties of In2-xCrxO3 Semiconductor Films by Ferroelectric Polarization Charge.

A series of Cr-doped In2-xCrxO3 (ICO) semiconductor thin films were epitaxially grown on (111)-oriented 0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3 (PMN-0.29PT) single-crystal substrates by the pulsed laser deposition. Upon the application of an electric field to the PMN-0.29PT substrate along the thickness direction, we realized in situ, reversible, and nonvolatile control of the electronic properties and Fermi level of the films, which are manifested by abundant physical phenomena such as the n-type to p-type transformation, metal-semiconductor transition, metal-insulator transition, crossover of the magnetoresistance (MR) from negative to positive, and a large nonvolatile on-and-off ratio of 5.5 × 104% at room temperature. We also strictly disclose that both the sign and the magnitude of MR are determined by the electron carrier density of ICO films, which could modify the s-d exchange interaction and weak localization effect. Our results demonstrate that the ferroelectric gating approach using PMN-PT can be utilized to gain deeper insight into the carrier-density-related electronic properties of In2O3-based semiconductors and provide a simple and energy efficient way to construct multifunctional devices which can utilize the unique properties of composite materials.

Nonvolatile and Reversible Ferroelectric Control of Electronic Properties of Bi2Te3 Topological Insulator Thin Films Grown on Pb(Mg1/3Nb2/3)O3-PbTiO3 Single Crystals.

Single-phase (00 l)-oriented Bi2Te3 topological insulator thin films have been deposited on (111)-oriented ferroelectric 0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3 (PMN-PT) single-crystal substrates. Taking advantage of the nonvolatile polarization charges induced by the polarization direction switching of PMN-PT substrates at room temperature, the carrier density, Fermi level, magnetoconductance, conductance channel, phase coherence length, and quantum corrections to the conductance can be in situ modulated in a reversible and nonvolatile manner. Specifically, upon the polarization switching from the positively poled Pr+ state (i.e., polarization direction points to the film) to the negatively poled Pr- (i.e., polarization direction points to the bottom electrode) state, both the electron carrier density and the Fermi wave vector decrease significantly, reflecting a shift of the Fermi level toward the Dirac point. The polarization switching from Pr+ to Pr- also results in significant increase of the conductance channel α from -0.15 to -0.3 and a decrease of the phase coherence length from 200 to 80 nm at T = 2 K as well as a reduction of the electron-electron interaction. All these results demonstrate that electric-voltage control of physical properties using PMN-PT as both substrates and gating materials provides a simple and a straightforward approach to realize reversible and nonvolatile tuning of electronic properties of topological thin films and may be further extended to study carrier density-related quantum transport properties of other quantum matter.

Integration of Oxide Semiconductor Thin Films with Relaxor-Based Ferroelectric Single Crystals with Large Reversible and Nonvolatile Modulation of Electronic Properties.

We report the fabrication of 0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3 (PMN-0.29PT)-based ferroelectric field effect transistors (FeFETs) by the epitaxial growth of cobalt-doped tin dioxide (SnO2) semiconductor thin films on PMN-0.29PT single crystals. Using such FeFETs we realized in situ, reversible, and nonvolatile manipulation of the electron carrier density and achieved a large nonvolatile modulation of the resistance (∼330%) of the SnO2:Co films through the polarization switching of PMN-0.29PT at 300 K. Particularly, combining the ferroelectric gating with piezoresponse force microscopy, X-ray diffraction, Hall effect, and magnetoresistance (MR), we rigorously disclose that both sign and magnitude of the MR are intrinsically determined by the electron carrier density, which could modify the s-d exchange interaction of the SnO2:Co films. Furthermore, we realized multilevel resistance states of the SnO2:Co films by combining the ferroelectric gating with ultraviolet light illumination, demonstrating that the FeFETs have potential applications in multistate resistive memories and electro-optical devices.

Semiconductor/Piezoelectrics Hybrid Heterostructures with Highly Effective Gate-Tunable Electrotransport and Magnetic Behaviors.

We report the epitaxial growth of oxygen deficient titanium dioxide thin films on 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 (PMN-PT) single crystals and realized highly effective in situ electrostatic manipulation of electrotransport and magnetism of TiO2-δ films via gate voltages. Upon the polarization switching in the PMN-PT, the carrier density of the TiO2-δ film could be reversibly modified, resulting in a large nonvolatile resistivity modulation by ∼51% at T = 300 K, approximately 4-12 times larger than that of other transition-metal oxide film/PMN-PT structures. By taking advantage of in situ manipulation of the carrier density via gate voltages, we found that competition between the trap of electrons by the Ti3+-VO pairs and that by the positive polarization charges at the interface results in a significant resistivity relaxation upon the polarization switching, and revealed that magnetization is inversely correlated with the carrier density of the TiO2-δ film. Such hybrid structures combining materials with dissimilar functionalities may have potential applications in multifunctional devices which can take advantage of the useful and unique properties of both materials.