Antiferromagnetism of Zn$_2$VO(PO$_4)_2$ and the dilution with Ti$^{4+}$

TL;DR

This study investigates the antiferromagnetic properties of Zn$_2$VO(PO$_4)_2$ and how non-magnetic Ti$^{4+}$ doping affects its magnetic order, revealing consistent long-range antiferromagnetic order and minimal structural distortion.

Contribution

It provides detailed experimental characterization of magnetic order and hyperfine interactions in Zn$_2$VO(PO$_4)_2$ and its Ti$^{4+}$ doped variants, with insights into the effects of doping on magnetic properties.

Findings

Long-range antiferromagnetic order below 3.8-3.9 K.

Hyperfine couplings determined from NMR measurements.

Doping causes a linear decrease in Néel temperature.

Abstract

We report static and dynamic properties of the antiferromagnetic compound Zn$_{2}$(VO)(PO$_{4}$)$_{2}$, and the consequences of non-magnetic Ti$^{4+}$ doping at the V$^{4+}$ site. $^{31}$P nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rate ($1/T_1$) consistently show the formation of the long-range antiferromagnetic order below $T_N= 3.8-3.9$\,K. The critical exponent $\beta=0.33 \pm 0.02$ estimated from the temperature dependence of the sublattice magnetization measured by $^{31}$P NMR at 9.4\,MHz is consistent with universality classes of three-dimensional spin models. The isotropic and axial hyperfine couplings between the $^{31}$P nuclei and V$^{4+}$ spins are $A_{\rm hf}^{\rm iso} = (9221 \pm 100)$ Oe/$\mu_{\rm B}$ and $A_{\rm hf}^{\rm ax} = (1010 \pm 50)$ Oe/$\mu_{\rm B}$, respectively. Magnetic susceptibility data above 6.5\,K and heat capacity data above 4.5\,K are well described by quantum Monte-Carlo simulations for the Heisenberg model on the square lattice with $J\simeq 7.7$\,K. This value of $J$ is consistent with the values obtained from the NMR shift, $1/T_1$ and electron spin resonance (ESR) intensity analysis. Doping Zn$_2$VO(PO$_4)_2$ with non-magnetic Ti$^{4+}$ leads to a marginal increase in the $J$ value and the overall dilution of the spin lattice. In contrast to the recent \textit{ab initio} results, we find neither evidence for the monoclinic structural distortion nor signatures of the magnetic one-dimensionality for doped samples with up to 15\% of Ti$^{4+}$. The N\'eel temperature $T_{\rm N}$ decreases linearly with increasing the amount of the non-magnetic dopant.