One-step synthesis of Cu-doped Pb$_{10}$(PO$_{4}$)$_{6}$Cl$_{2}$ apatite: A wide-gap semiconductor

TL;DR

This study presents a simple one-step synthesis method for Cu-doped Pb$_{10}$(PO$_{4}$)$_{6}$Cl$_{2}$, demonstrating it is a wide-gap semiconductor without superconductivity, contrary to previous claims.

Contribution

The paper introduces a straightforward synthesis approach for Cu-doped Pb$_{10}$(PO$_{4}$)$_{6}$Cl$_{2}$ and clarifies Cu's preferred location, challenging earlier superconductivity claims.

Findings

Cu doping causes lattice expansion in Pb$_{10}$(PO$_{4}$)$_{6}$Cl$_{2}$.

All samples are wide-gap semiconductors with gaps of 4.46-4.59 eV.

Cu-doped samples show paramagnetic behavior without superconductivity.

Abstract

The recent claim of potential room-temperature superconductivity in Pb$_{10-x}$Cu$_{x}$(PO$_{4}$)$_{6}$O has attracted widespread attention. However, the signature of superconductivity is later attributed to the Cu$_{2}$S impurity formed during the multiple-step synthesis procedure. Here we report a simple one-step approach to synthesize single-phase chloride analogue Cu-doped Pb$_{10}$(PO$_{4}$)$_{6}$Cl$_{2}$ using PbO, PbCl$_{2}$, CuCl$_{2}$, and NH$_{4}$H$_{2}$PO$_{4}$ as starting materials. Irrespective of the initial stoichiometry, the Cu doping always leads to a lattice expansion in Pb$_{10}$(PO$_{4}$)$_{6}$Cl$_{2}$. This indicates that Cu prefers to reside in the hexagonal channels rather than substitutes at the Pb site, and the chemical formula is expressed as Pb$_{10}$(PO$_{4}$)$_{6}$Cu$_{x}$Cl$_{2}$. All the Pb$_{10}$(PO$_{4}$)$_{6}$Cu$_{x}$Cl$_{2}$ (0 $\leq$ $x$ $\leq$ 1.0) samples are found to be semiconductors with wide band gaps of 4.46-4.59 eV, and the Cu-doped ones ($x$ = 0.5 and 1.0) exhibit a paramagnetic behavior without any phase transition between 400 and 1.8 K. Our study calls for a reinvestigation of the Cu location in Pb$_{10-x}$Cu$_{x}$(PO$_{4}$)$_{6}$O, and supports the absence of superconductivity in this oxyapatite.