Anisotropic character of the metal-to-metal transition in $\mathrm{P}{\mathrm{r}}_4\mathrm{N}{\mathrm{i}}_3{\mathrm{O}}_{10}$

As a member of the Ruddlesden-Popper $L{n}_{\mathrm{n}+1}\mathrm{N}{\mathrm{i}}_{\mathrm{n}}{\mathrm{O}}_{3\mathrm{n}+1}$ series rare-earth-nickelates, $\mathrm{P}{\mathrm{r}}_4\mathrm{N}{\mathrm{i}}_3{\mathrm{O}}_{10}$ consists of infinite quasi-two-dimensional perovskite-like Ni-O based layers. Although a metal-to-metal phase transition at $T_{pt}\approx 157\mathrm{K}$ has been revealed by previous studies, a comprehensive study of physical properties associated with this transition has not yet been performed. We have grown single crystals of $\mathrm{P}{\mathrm{r}}_4\mathrm{N}{\mathrm{i}}_3{\mathrm{O}}_{10}$ at high oxygen pressure, and report on the physical properties around that phase transition, such as heat-capacity, electric-transport, and magnetization. We observe a distinctly anisotropic behavior between in-plane and out-of-plane properties: a metal-to-metal transition at $T_{pt}$ within the a-b plane, and a metal-to-insulator-like transition along the $c$ axis with decreasing temperature. Moreover, an anisotropic and anomalous negative magnetoresistance is observed at $T_{pt}$ that we attribute to a slight suppression of the first-order transition with magnetic field. The magnetic susceptibility can be well described by a Curie-Weiss law, with different Curie constants and Pauli-spin susceptibilities between the high-temperature and the low-temperature phases. The single crystal x-ray diffraction measurements show a shape variation of the different $\mathrm{Ni}{\mathrm{O}}_6$ octahedra from the high-temperature phase to the low-temperature phase. This subtle change of the environment of the Ni sites is likely responsible for the different physical properties at high and low temperatures.

Figure 1

(a) Illustration of the layered crystal structure of $\mathrm{P}{\mathrm{r}}_4\mathrm{N}{\mathrm{i}}_3{\mathrm{O}}_{10}$; (b) (0kl), (h0k) and (hk0) planes (from left to right) of single crystal $\mathrm{P}{\mathrm{r}}_4\mathrm{N}{\mathrm{i}}_3{\mathrm{O}}_{10}$ based on a single crystal diffraction experiment performed at 150(1) K ($P{2}_1/a$ settings); (c) Experimental powder XRD ($\mathrm{Cu}{K}_{\alpha 1}$ radiation) pattern (red crosses) for pulverized single crystal sample of $\mathrm{P}{\mathrm{r}}_4\mathrm{N}{\mathrm{i}}_3{\mathrm{O}}_{10}$ at room temperature. The black line corresponds to the best fit from the Rietveld refinement analysis. Lower vertical marks denote the Bragg peak positions. The bottom, grey line represents the difference between experimental and calculated points; the inset of (c) shows the image of the crystal used for all the measurements.

Figure 2

(a) Temperature dependence of heat-capacity of $\mathrm{P}{\mathrm{r}}_4\mathrm{N}{\mathrm{i}}_3{\mathrm{O}}_{10}$ between 10 and 300 K. Inset: $C/T$ as a function of temperature around $T_{pt}$; (b) Corresponding entropy S(T), showing a steplike feature at $T_{pt}$.

Figure 3

Temperature dependence of the normalized zero-field resistivities of $\mathrm{P}{\mathrm{r}}_4\mathrm{N}{\mathrm{i}}_3{\mathrm{O}}_{10}$, both in-plane (${\rho }_{\parallel }$) and out-of-plane (${\rho }_{\perp }$); the inset shows resistivity data ${\rho }_{\parallel }$ around $T_{pt}$ of both the normalized resistivity and its derivative, as functions of temperature.

Figure 4

The magnetoresistivity measurements of $\mathrm{P}{\mathrm{r}}_4\mathrm{N}{\mathrm{i}}_3{\mathrm{O}}_{10}$ for both in-plane (a) and out-of-plane (b) configurations, plotted vs. $B^2$ for clarity; (c) and (d) show the respective temperature dependences of the magnetoresistivities for $B=9\mathrm{T}$.

Figure 5

Field-cooling (FC) magnetic susceptibility of $\mathrm{P}{\mathrm{r}}_4\mathrm{N}{\mathrm{i}}_3{\mathrm{O}}_{10}$ and its derivative in an external magnetic field $B=0.1\mathrm{T}$ near the phase transition for $B\parallel c$ (a) and $B\perp c$ (b); Magnetic-susceptibility data with Néel-type fits above and below $T_{pt}$ for $B\parallel c$ (c) and $B\perp c$ (d); $\mathrm{\Delta }\chi$ corresponds to the steplike increase of the magnetic susceptibility from the low-temperature to the high-temperature phase; the corresponding zero-field cooling (ZFC) data overlap with no detectable hysteresis and are therefore not shown for clarity.