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Physical Review Letters

Spin dynamics and electronic states of N-Vcenters in diamond by EPR and four-wave-mixing spectroscopy

David A. Redman, S. Brown, Richard H. Sands, Stephen Colby Rand

Published Dec 9, 1991• 166 citations
Publisher

Abstract

A new phase-modulation technique for nonlinear laser spectroscopy is applied with a relative resolving power in the sub-Hz range to measure fundamental relaxation processes of the N-V center in diamond. Complementary EPR experiments versus temperature establish the spin character of the ground state in the absence of optical illumination and show that spin-lattice decay occurs via two-phonon processes involving the dominant vibrational mode. The combined results permit deduction of reliable fine-structure assignments for three states of the center and accurate values for zero-field intersystem crossing and spin-lattice relaxation rates from linewidths of individual resonances in the four-wave-mixing spectrum.

DOI
10.1103/physrevlett.67.3420

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Electronic structure of the N-Vcenter in diamond: Experiments

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Quantum-beat spectroscopy has been used to observe excited states of the N-V center in diamond. For the 1.945-eV optical transition, direct evidence is presented for the existence of GHz-scale fine structure, together with a much larger 46-${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$ level splitting in the E state. An interference effect observed in transient four-wave-mixing response is explained with a polarization selection rule involving Zeeman coherence among magnetic sublevels. Also, detailed dephasing measurements versus temperature and wavelength have identified the decay mechanisms operative among the various states. A comparison of these results with ab initio calculations of excited electronic structure and interactions based on several multielectron models supports the conclusion that the N-V center is a neutral, two-electron center governed by a strong Jahn-Teller effect and weak spin-spin interactions. \textcopyright{} 1996 The American Physical Society.

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Electronic structure of the nitrogen-vacancy color center in diamond.

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The nitrogen - vacancy (N-V) center is a point defect found in diamonds containing substitutional nitrogen impurities. It arises after exposure to ionizing radiation and subsequent thermal annealing. The physical structure of the center has previously been identified as a substitutional nitrogen atom located adjacent to a neutral carbon vacancy, but prior to this work knowledge of its electronic structure was very incomplete. The results presented here are intended to establish the energy level structure of the N-V center unambiguously, using nonlinear laser spectroscopy in concert with paramagnetic resonance experiments. A new technique which achieves sub-Hertz resolution in nearly degenerate four-wave mixing (NDFWM) and optical two-beam coupling experiments was applied to determine the decay rates of excited states in the N-V center. Laser-enhanced EPR experiments were performed to assign spin character to the ground state. Fluorescent emission of the center was used to determine excited state energies. In particular, these results resolve earlier conflicting reports of the N-V ground state structure and offer a picture of state energies and dynamics consistent with all observations to date. The principal results of this thesis may be summarized as follows. We show that the ground state of the center consists of a spin triplet ground state with a zero-field splitting of 2.88 GHz and a spin-lattice relaxation time of 1.170 $\pm$ 0.003 ms. The first parity-allowed transition occurs to a triplet excited state at 1.944 eV with a lifetime of 13.3 $\pm$ 0.2 ns. The first metastable singlet excited state is shown to have a lifetime of 265.3 $\pm$ 0.6 ms at room temperature and its temperature dependence measured between 77 and 295 K. Through low temperature studies the mechanism for ground state spin-lattice relaxation is determined to be a two-phonon process involving 63 meV optical phonons. Finally, the origin of satellite lines in the persistent hole-burning spectrum is tentatively explained using our picture of the energy level structure and used to infer a zero-field spin splitting in the excited triplet state of 0.6 GHz.

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Upon the cw optical excitation of N-V centers in diamond, a spin alignment in the ensemble of nonexcited N-V defects in the electron spin-triplet ground state is induced. When the diamond sample is subjected to magnetic fields of suitable directions and strengths, cross relaxation (CR) and level anticrossing are found to affect the ground-state spin alignment as well as the intensity of the emission due to the photoexcited N-V centers. In this paper, a study of the dynamics involved in the cross-relaxation and autocrossing processes is reported, utilizing techniques for the optical detection of spin-coherent transients. A major finding is that when CR conditions prevail, the stimulated spin-echo and spin-locking signals decay at a rate about three times faster than in the situation in which CR does not occur. The results are accounted for by considering the magnetic dipole-dipole interactions within the ensemble of N-V centers in the triplet ground state in a memory function approach.

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Alexander P. Nizovtsev, S. Ya. Kilin, Fedor Jelezko +4 more

The spin-selective photokinetics of a single matrix-isolated impurity molecule with a triplet-triplet optical transition, T 0–T 1, is considered and the manifestations of the photokinetics in the fluorescence excitation spectra and intensity autocorrelation functions g (2)(τ) of the molecule undergoing narrow-band optical excitation is studied to resolve the fine structure of the transition. The rates of intersystem crossings (ISCs) T 1→S→T 0 to and from a nonradiating singlet state S of the molecule and the rate of population relaxation among the ground (T 0) state sublevels can be obtained from the spectra and g (2)(τ) using the analytical expressions obtained. New experiments on an individual NV defect center in nanocrystals of diamond, where, for the first time, the fine structure of its triplet-triplet 3 A-3 E zero-phonon optical transition (~637 nm) at 1.4 K was resolved, are interpreted. It is concluded that the rate of the ISC transition from the m S =0 sublevel of the excited 3 E state to the singlet 1 A state (~1 kHz) is much slower than the rates from the m S =±1 substates, while the rates of ISC transitions to different m S substates of the ground 3 A state are close to each other (~1 Hz). As a result, only the optical transition between m S =0 sublevels in the 3 A-3 E manifold contributes strongly to the fluorescence. The experimentally observed double-exponential decay of the g (2)(τ) function is explained by the two pathways available to the center for it to leave the S state: (i) the S→ T 0(m S )=0) transition and (ii) the S→T 0(m S =±1) transitions followed by the slow spin-lattice relaxation T 0(m S =±1)→T 0(m S =0) (rate ~0.1 Hz). The work is important for studies where the NV center is used as a single photon source or for quantum information processing.

Optics and Spectroscopy•Jun 1, 2003•42 citations
A new phase-modulation technique for nonlinear laser spectroscopy is applied with a relative resolving power in the sub-Hz range to measure fundamental relaxation processes of the N-V center in diamond. Complementary EPR experiments versus temperature establish the spin character of the ground state in the absence of optical illumination and show that spin-lattice decay occurs via two-phonon processes involving the dominant vibrational mode. The combined results permit deduction of reliable fine-structure assignments for three states of the center and accurate values for zero-field intersystem crossing and spin-lattice relaxation rates from linewidths of individual resonances in the four-wave-mixing spectrum.
Quantum-beat spectroscopy has been used to observe excited states of the N-V center in diamond. For the 1.945-eV optical transition, direct evidence is presented for the existence of GHz-scale fine structure, together with a much larger 46-${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$ level splitting in the E state. An interference effect observed in transient four-wave-mixing response is explained with a polarization selection rule involving Zeeman coherence among magnetic sublevels. Also, detailed dephasing measurements versus temperature and wavelength have identified the decay mechanisms operative among the various states. A comparison of these results with ab initio calculations of excited electronic structure and interactions based on several multielectron models supports the conclusion that the N-V center is a neutral, two-electron center governed by a strong Jahn-Teller effect and weak spin-spin interactions. \textcopyright{} 1996 The American Physical Society.
The nitrogen - vacancy (N-V) center is a point defect found in diamonds containing substitutional nitrogen impurities. It arises after exposure to ionizing radiation and subsequent thermal annealing. The physical structure of the center has previously been identified as a substitutional nitrogen atom located adjacent to a neutral carbon vacancy, but prior to this work knowledge of its electronic structure was very incomplete. The results presented here are intended to establish the energy level structure of the N-V center unambiguously, using nonlinear laser spectroscopy in concert with paramagnetic resonance experiments. A new technique which achieves sub-Hertz resolution in nearly degenerate four-wave mixing (NDFWM) and optical two-beam coupling experiments was applied to determine the decay rates of excited states in the N-V center. Laser-enhanced EPR experiments were performed to assign spin character to the ground state. Fluorescent emission of the center was used to determine excited state energies. In particular, these results resolve earlier conflicting reports of the N-V ground state structure and offer a picture of state energies and dynamics consistent with all observations to date. The principal results of this thesis may be summarized as follows. We show that the ground state of the center consists of a spin triplet ground state with a zero-field splitting of 2.88 GHz and a spin-lattice relaxation time of 1.170 ±\pm± 0.003 ms. The first parity-allowed transition occurs to a triplet excited state at 1.944 eV with a lifetime of 13.3 ±\pm± 0.2 ns. The first metastable singlet excited state is shown to have a lifetime of 265.3 ±\pm± 0.6 ms at room temperature and its temperature dependence measured between 77 and 295 K. Through low temperature studies the mechanism for ground state spin-lattice relaxation is determined to be a two-phonon process involving 63 meV optical phonons. Finally, the origin of satellite lines in the persistent hole-burning spectrum is tentatively explained using our picture of the energy level structure and used to infer a zero-field spin splitting in the excited triplet state of 0.6 GHz.
The nitrogen-vacancy center in diamond exhibits a zero-phonon transition art 637 nm that has been assigned as an A→E transition at a site with trigonal symmetry.1 Paramagnetic resonance studies revealed a triplet feature that was originally assigned to an excited state.2 More recently, it was argued that the triplet signal actually arose from the ground state,3,4We employ a new method of ultra-high-resolution nearly degenerate four-wave-mixing (NDFWM) spectroscopy, as well as persistent hole burning and electron paramagnetic resonance, to measure the metastable spin singlet excited-state lifetime and the g round-state spin-lattice relaxation time and also to prove that the ground state is indeed a triplet.
Upon the cw optical excitation of N-V centers in diamond, a spin alignment in the ensemble of nonexcited N-V defects in the electron spin-triplet ground state is induced. When the diamond sample is subjected to magnetic fields of suitable directions and strengths, cross relaxation (CR) and level anticrossing are found to affect the ground-state spin alignment as well as the intensity of the emission due to the photoexcited N-V centers. In this paper, a study of the dynamics involved in the cross-relaxation and autocrossing processes is reported, utilizing techniques for the optical detection of spin-coherent transients. A major finding is that when CR conditions prevail, the stimulated spin-echo and spin-locking signals decay at a rate about three times faster than in the situation in which CR does not occur. The results are accounted for by considering the magnetic dipole-dipole interactions within the ensemble of N-V centers in the triplet ground state in a memory function approach.
The spin-selective photokinetics of a single matrix-isolated impurity molecule with a triplet-triplet optical transition, T 0–T 1, is considered and the manifestations of the photokinetics in the fluorescence excitation spectra and intensity autocorrelation functions g (2)(τ) of the molecule undergoing narrow-band optical excitation is studied to resolve the fine structure of the transition. The rates of intersystem crossings (ISCs) T 1→S→T 0 to and from a nonradiating singlet state S of the molecule and the rate of population relaxation among the ground (T 0) state sublevels can be obtained from the spectra and g (2)(τ) using the analytical expressions obtained. New experiments on an individual NV defect center in nanocrystals of diamond, where, for the first time, the fine structure of its triplet-triplet 3 A-3 E zero-phonon optical transition (~637 nm) at 1.4 K was resolved, are interpreted. It is concluded that the rate of the ISC transition from the m S =0 sublevel of the excited 3 E state to the singlet 1 A state (~1 kHz) is much slower than the rates from the m S =±1 substates, while the rates of ISC transitions to different m S substates of the ground 3 A state are close to each other (~1 Hz). As a result, only the optical transition between m S =0 sublevels in the 3 A-3 E manifold contributes strongly to the fluorescence. The experimentally observed double-exponential decay of the g (2)(τ) function is explained by the two pathways available to the center for it to leave the S state: (i) the S→ T 0(m S )=0) transition and (ii) the S→T 0(m S =±1) transitions followed by the slow spin-lattice relaxation T 0(m S =±1)→T 0(m S =0) (rate ~0.1 Hz). The work is important for studies where the NV center is used as a single photon source or for quantum information processing.