Nitrogen acceptor in 2H-polytype synthetic MoS2 assessed by multifrequency electron spin resonance

Abstract

Electron spin resonance (ESR) study on 2H-polytype synthetic MoS2 revealed the N acceptor dopants as being characterized by a spectrum of axial symmetry [g∥ = 2.032(2); g⊥ = 2.270(2)], typical for a hole-type center in MoS2. The N impurities substitute for S sites, with a density of ∼2.3 × 1017 cm−3, which accounts for the overall p-type doping. With respect to measurements for the applied magnetic field directed along the c-axis, the signal consists of a 14N primary hyperfine triplet of splitting constant A∥ = 14.7 ± 0.2 G superimposed on a correlated Gaussian single central line of peak-to-peak width ΔBpp = 15.3 ± 0.5 G, the latter making up only ∼26% of the total signal intensity. The current work extends on these results through extensive monitoring of the temperature (T) dependence of salient ESR parameters and studying the impact of thermal treatment. ESR signal saturation studies indicate a N acceptor spin–lattice relaxation time T1 (4.2 K) ≈ 3 × 10−4 s, notably different from the much smaller As acceptor’s T1 in geological MoS2. Concerning the thermal stability of the dopant, the N acceptor is found to be drastically passivated when exposed to H2 at ∼500 °C. Yet, subsequent reactivation attempts in vacuum at temperatures up to 740 °C appear unsuccessful, urging great caution with conventional forming gas treatments at T ≳ 500 °C. Combination of careful K- and Q-band ESR monitoring of the T-dependent signal intensity resulted in the consolidation of the N dopant as a shallow acceptor of activation energy Ea = 45 ± 7 meV. The consolidated results establish N as a promising candidate for stable covalently bonded p-type doping of MoS2 layers intended for application in novel nanoelectronic devices.