Tuning electronic properties of hydroxyapatite through controlled doping using zinc, silver, and praseodymium: A density of states and experimental study

This study presents a comprehensive exploration of the electronic properties of hydroxyapatite (HA) doped with zinc (Zn), silver (Ag), and praseodymium (Pr). Five distinct compositions-0.4Pr-HA, 0.4Zn-0.4Pr-HA, 0.8Zn0.4Pr-HA, 0.4Ag-0.4Pr-HA, and 0.8Zn-0.4Pr-HA were systematically investigated through Density of States (DOS) and band structure calculations. The computed band gap values, ranging from 4.4037 to 4.1554 eV, revealed a progressive decrease in band gap energy from 0.4Pr-HA to 0.8Ag-0.4Pr-HA, emphasizing the substantial impact of dopant composition on electronic properties. Additionally, the incorporation of Pr induced distinct bands and peaks in the density of states, signifying the emergence of specific energy levels associated with Pr and suggesting a clear effect on the electronic structure. Furthermore, the study explores the influences of dopant type and quantity on the electronic structure, microstructure, spectral, thermal, and in vitro cell viability properties of Pr-based HA samples. Theoretical results demonstrated a continuous decrease in the bandgap with Ag or Zn dopants, and the study observed controllable changes in LAC values based on co-dopant type and quantity. Experimental outcomes revealed significant effects on crystallinity, crystallite size, lattice parameters, and unit cell volume, confirmed through XRD, SEM, EDX, FTIR, and Raman analyses. These findings provide valuable visions into the tunability of the electronic properties of HA through controlled doping with Zn, Pr, and Ag. This knowledge is crucial for modifying materials with desirable electronic properties, and thus holds promise for various applications in electronic devices and biocompatible coatings.