Materials and Spin Characteristics of Nanodiamonds Partially Covered with Amino Groups and Embedded with Nitrogen-Vacancy Color Centers.

Fluorescent nanodiamonds (FNDs) with optically read qubits hold great potential for detecting electric and magnetic fields, temperature, and other nanoscale physicochemical quantities relevant to chemistry and biology. Proper surface functionalization is essential for their application as probes, but surface modifications can impact qubit sensor properties. In this work, we systematically study nitrogen-vacancy (NV) color centers in FNDs as a function of size and surface termination. FNDs were produced from high-pressure, high-temperature diamonds, with NV centers introduced via electron irradiation and annealing. The initial oxygen-covered FNDs were homogenized with hydroxyl (-OH) groups as reference samples, while the noninvasive Hofmann degradation introduced amino (-NH2) groups for potential direct biomolecule attachment. Although amino groups may not homogeneously cover these nanodiamonds, we simply label them as -NH2 terminated FNDs in this context. We monitored charge state stability and the zero-field splitting parameters of the embedded NV centers. This study yields two principal advances. First, we resolve the size dependence of the NV(-) zero-field splitting parameters across the 10-140 nm range and show that the symmetry-breaking E parameter decreases monotonically from ∼8 to ∼5 MHz with increasing size while the axial D parameter is shifted only in the smallest (≤30 nm) particles, thereby disentangling the static-strain and fluctuating electric-field contributions to the spin levels. Second, while NV charge state stabilization was observed in both -OH- and -NH2-terminated FNDs above a certain size, we demonstrate that a remarkably high and laser-power-independent NV(-) content (f NV(-) ≈ 0.8) is achieved by wet-chemical Hofmann amino termination only in 140 nm particles, an effect we link through electron spin resonance to the degradation of surface paramagnetic defects rather than to the introduction of new ones.