Study of Integer Spin S = 1 in the Polar Magnet ß-Ni(IO3)2.

Polar magnetic materials exhibiting appreciable asymmetric exchange interactions can potentially host new topological states of matter such as vortex-like spin textures; however, realizations have been mostly limited to half-integer spins due to rare numbers of integer spin systems with broken spatial inversion lattice symmetries. Here, we studied the structure and magnetic properties of the S = 1 integer spin polar magnet ß-Ni(IO3)2 (Ni2+, d8, 3F). We synthesized single crystals and bulk polycrystalline samples of ß-Ni(IO3)2 by combining low-temperature chemistry techniques and thermal analysis and characterized its crystal structure and physical properties. Single crystal X-ray and powder X-ray diffraction measurements demonstrated that ß-Ni(IO3)2 crystallizes in the noncentrosymmetric polar monoclinic structure with space group P21. The combination of the macroscopic electric polarization driven by the coalignment of the (IO3)- trigonal pyramids along the b axis and the S = 1 state of the Ni2+ cation was chosen to investigate integer spin and lattice dynamics in magnetism. The effective magnetic moment of Ni2+ was extracted from magnetization measurements to be 3.2(1) µB, confirming the S = 1 integer spin state of Ni2+ with some orbital contribution. ß-Ni(IO3)2 undergoes a magnetic ordering at T = 3 K at a low magnetic field, µ0H = 0.1 T; the phase transition, nevertheless, is suppressed at a higher field, µ0H = 3 T. An anomaly resembling a phase transition is observed at T ≈ 2.7 K in the Cp/T vs. T plot, which is the approximate temperature of the magnetic phase transition of the material, indicating that the transition is magnetically driven. This work offers a useful route for exploring integer spin noncentrosymmetric materials, broadening the phase space of polar magnet candidates, which can harbor new topological spin physics.

LiMII (IO3 )3 (MII =Zn and Cd): Two Promising Nonlinear Optical Crystals Derived from a Tunable Structure Model of α-LiIO3.

Excellent nonlinear optical materials simultaneously meet the requirements of large SHG response, phase-matching capability, wide transparency windows, considerable energy band-gap, good thermal stability and structure stability. Herein, two new promising nonlinear optical (NLO) crystals LiMII (IO3 )3 (MII =Zn and Cd) are rationally designed by the aliovalent substitution strategy from the commercialized α-LiIO3 with the perfect parallel alignment of IO3 groups. Compared with parent α-LiIO3 and related AI 2 MIV (IO3 )6 , the title compounds exhibit more stable covalent 3D structure, and overcome the racemic twinning problem of AI 2 MIV (IO3 )6 . More importantly, both compounds inherit NLO-favorable structure merits of α-LiIO3 and show larger SHG response (≈14× and ≈12×KDP), shorter absorption edge (294 and 297 nm) with wider energy band-gap (4.21 and 4.18 eV), good thermal stability (460 and 430 °C), phase-matching behaviors, wider optical transparency window and good structure stability, achieving an excellent balance of NLO properties.

Wide-Bandgap Rare-Earth Iodate Single Crystals for Superior X-Ray Detection and Imaging.

Semiconductor-based X-ray detectors with low detectable thresholds become critical in medical radiography applications. However, their performance is generally limited by intrinsic defects or unresolved issues of materials, and developing a novel scintillation semiconductor for low-dose X-ray detection is a highly urgent objective. Herein, a high-quality rare-earth iodate Tm(IO3 )3 single crystal grown through low-cost solution processing is reported with a wide bandgap of 4.1 eV and a large atomic number of 53.2. The roles of IO and TmO groups for charge transport in the Tm(IO3 )3 are revealed with the structural difference between the [101] and [ 1 ¯ 01 ] $[{\bar{1}}01]$ crystal orientations. Based on anisotropic responses of material properties and detection performances, it is found that the [ 1 ¯ 01 ${\bar{1}}01$ ] orientation, the path with fewer IO groups, achieves a high resistivity of 1.02 × 1011 Ω cm. Consequently, a single-crystal detector exhibits a low dark current and small baseline drifting due to the wide bandgap, high resistivity and less ion migration of Tm(IO3 )3 , resulting in a low detection limit of 85.2 nGyair s-1 . An excellent X-ray imaging performance with a high sensitivity of 4406.6 µC Gyair -1 cm-2 is also shown in the Tm(IO3 )3 device. These findings provide a new material design perspective for high-performance X-ray imaging applications.