Symmetry of the phosphorus donor in diamond from first principles

Abstract

Phosphorus is the only donor in diamond which can be used technologically. Several ab initio theoretical models have been published on substitutional phosphorus, and most of them have predicted that it should have tetrahedral or trigonal symmetry. Recent ab initio calculations suggested that C 2v , C 3v , and D 2d conformations reduce the total energy. Electron-paramagnetic-resonance experiments performed on phosphorus-doped diamond revealed a phosphorus-related center with tetragonal symmetry, although the signal is only observed below 20 K. We present a detailed ab initio study to show that the phosphorus substitutional atom has tetragonal symmetry at low temperatures. A study of the vibrational modes allows us to investigate the Jahn-Teller origin of the tetragonal distortion and to predict the solubility of phosphorus when grown by chemical vapor deposition with phosphine in the gas phase.

Phosphorus‐Related Complexes and Shallow Doping in Diamond

“…The unpaired electron will be accommodated in one singlet ( b 2 ) state. As Figure (a) shows, the highest occupied molecular orbital has b 2 symmetry, in accordance with Butorac and Mainwood . Our calculations show that the ϵ (0/+) is located at E V + 4.20 eV, in agreement with the literature .…”

“…As Figure 1(a) shows, the highest occupied molecular orbital has b 2 symmetry, in accordance with Butorac and Mainwood. [12] Our calculations show that the e(0/þ) is located at E V þ 4.20 eV, in agreement with the literature. [1] Increase of the MP mesh did not lead to any significant change of e(0/þ) energy position (E V þ 4.25 eV).…”

“…Substitutional P (P C ) was examined in either T d or D 2d symmetry. Similarly to what reported in the literature, [12] we found that the D 2d structure is the most energetically stable one. After geometry relaxation the P-C bond length is 1.70 Å (Figure 1 (a)) and the C-P-C bond angles become 120 and 105 .…”

Features of free carrier and exciton recombination, diffusion, and photoluminescence in undoped and phosphorus-doped diamond layers

“…The energy level of a phosphorous-related donor, as derived from the D-A recombination spectra observed in phosphorous doped CVD diamond films, was known to be E D = 0.65 eV[46] (the lower value of 0.58 eV in the studied sample was obtained by Hall measurements[7]). Phosphorus excited states were calculated theoretically to be at 0.58, 0.48, 0.43, 0.39 eV below the conduction band[47]. Much stronger emission, observed from the excited state with respect to the ground one, can be explained by very slow excited state relaxation to the ground state (similar effect was observed in B-N doped diamond[48] for boron impurity).…”

Towards a Room-Temperature Spin Quantum Bus in Diamond via Electron Photoionization, Transport, and Capture

“…As per the N S center, in the neutral charge state P 0 S , one of these levels is occupied by an electron, whereas in the positive charge state P þ S , they are unoccupied [83][84][85]. It may be possible for NV-P S clusters to be created in a similar way as NV-N S clusters via N-P codoping or coimplantation.…”