Nitrogen-vacancy (NV) centers in diamond exist in neutral (NV0) and negatively charged (NV-) states, and quantifying their respective photoluminescence (PL) contributions is important for charge-state-based measurements. Existing methods either require additional experimental control or may suffer from limited physical identifiability. Here, we introduce a geometric method for determining NV charge-state contributions from PL spectra acquired at different excitation intensities. Each spectrum is mapped into a low-dimensional space through broadband spectral weighting, where changes in the relative NV0 and NV- contributions trace a one-dimensional trajectory. Zero-phonon-line (ZPL) information from two spectra physically calibrates this trajectory, enabling the NV-PL contribution to be determined by geometric projection. Measurements on two bulk single-crystal diamond samples yielded NV- contributions in close agreement with those obtained using an independent dual-excitation reference-spectrum method, with root-mean-square errors of 1.11 and 0.31 percentage points. Under additive spectral noise, the proposed method exhibited more than an order of magnitude less variation than a ZPL-only method. Fisher-information analysis further showed that the three-dimensional CIE XYZ representation retained approximately 81% of the information about the NV- contribution available in the full spectrum. These results establish a physically calibrated approach to low-dimensional spectral estimation that combines reduced experimental overhead with robust parameter estimation and provides a general framework for spectral sensing governed by a small number of physical degrees of freedom.
Nitrogen-vacancy (NV) centers in diamond exist in neutral (NV0) and negatively charged (NV-) states, and quantifying their respective photoluminescence (PL) contributions is important for charge-state-based measurements. Existing methods either require additional experimental control or may suffer from limited physical identifiability. Here, we introduce a geometric method for determining NV charge-state contributions from PL spectra acquired at different excitation intensities. Each spectrum is mapped into a low-dimensional space through broadband spectral weighting, where changes in the relative NV0 and NV- contributions trace a one-dimensional trajectory. Zero-phonon-line (ZPL) information from two spectra physically calibrates this trajectory, enabling the NV-PL contribution to be determined by geometric projection. Measurements on two bulk single-crystal diamond samples yielded NV- contributions in close agreement with those obtained using an independent dual-excitation reference-spectrum method, with root-mean-square errors of 1.11 and 0.31 percentage points. Under additive spectral noise, the proposed method exhibited more than an order of magnitude less variation than a ZPL-only method. Fisher-information analysis further showed that the three-dimensional CIE XYZ representation retained approximately 81% of the information about the NV- contribution available in the full spectrum. These results establish a physically calibrated approach to low-dimensional spectral estimation that combines reduced experimental overhead with robust parameter estimation and provides a general framework for spectral sensing governed by a small number of physical degrees of freedom.
Nitrogen vacancy (NV) centers in diamond are at the heart of many emerging quantum technologies, all of which require control over the NV charge state. Hence, methods for quantification of the relative photoluminescence intensities of the NV0 and NV− charge states, i.e., a charge state ratio, are vital. Several approaches to quantify NV charge state ratios have been reported but are either limited to bulk-like NV diamond samples or yield qualitative results. We propose an NV charge state quantification protocol based on the determination of sample- and experimental setup-specific NV0 and NV− reference spectra. The approach employs blue (400–470 nm) and green (480–570 nm) excitation to infer pure NV0 and NV− spectra, which are then used to quantify NV charge state ratios in subsequent experiments via least squares fitting. We test our dual excitation protocol (DEP) for a bulk diamond NV sample and 20 and 100 nm nanodiamond particles and compare results with those obtained via other commonly used techniques such as zero-phonon line fitting and non-negative matrix factorization. We find that DEP can be employed across different samples and experimental setups and yields consistent and quantitative results for NV charge state ratios that are in agreement with our understanding of NV photophysics. By providing robust NV charge state quantification across sample types and measurement platforms, DEP will support the development of NV-based quantum technologies.
Nitrogen-vacancy (NV) centers in single-crystal CVD diamond are promising candidates for quantum sensing due to their remarkable optical and spin properties [1]. These defects exhibit stable photoluminescence (PL), long spin coherence times, and high sensitivity to external fields [2]. In this study, we present a room-temperature PL characterization of NV centers excited with a 532 nm laser. The setup was optimized for high signal-to-noise ratio and spectral resolution. Key parameters analyzed include emission intensity, zero-phonon line (ZPL) at ~637 nm, phonon sidebands, and the charge state distribution between NV⁰ and NV⁻. The NV⁻ state, crucial for spin-based sensing, is evaluated to understand its stability under different nitrogen doping conditions [3]. The relative intensities of NV⁰ and NV⁻ provide insights into nitrogen incorporation and vacancy formation. These results contribute to optimizing synthesis conditions for enhanced NV⁻ concentration, supporting the advancement of diamond-based quantum sensing technologies.
We discuss charge state ratio-dependent spectral and temporal emission properties of nitrogen-vacancy (NV) centers in bulk diamonds. An understanding of the charge state ratio in artificially grown diamonds is important to design them for NV-based magnetometry. We show that the NV charge state ratio strongly correlates with the intensity of the zero-phonon line (ZPL) of NV−, which is supported by an emission dip at 2.87 GHz in spin-selective optical transitions. The Debye–Waller factor of NV centers depends on the charge state ratio, and it increases for NV− with an increase in the charge state ratio. We observe that the energy separation between the second phonon sideband (PSB) and ZPL does not scale multiplicatively with that of the energy separation between first PSB and ZPL. This deviation becomes more pronounced with an increase in charge state ratio, suggesting anharmonicity of vibrational energy levels, rather than the usually reported harmonicity. Further, we discuss the inherent relation between decay rates and charge states as a function of emission wavelengths. The excited state lifetime of NV0 remains constant, whereas the NV− lifetime decreases with an increase in the charge state ratio, with an overall decrease of 37%. Our results show an emission spectra-based approach to estimate the charge state ratio in diamond crystals, which is helpful for quantum-enhanced sensing and magnetometry.
Abstract The ultraviolet-visible (UV-Vis) spectrum was not generally considered an available method for measuring the concentration of negatively charged nitrogen-vacancy (NV-, NV center). In this study, we propose the idea of evaluating the concentration of NV center by the slope of the UV-Vis spectrum. To establish this new method we synthesized diamonds with different NV center concentrations by the chemical vapor deposition (CVD) method. We then measured the zero-phonon line (ZPL) intensity of PL spectra at 637 nm and estimated the concentration of the NV centers as a baseline for comparison to our new UV-Vis method. The UV-Vis transmission spectra were then measured and transformed to relative absorption coefficient spectra. Slopes of the transformed UV-Vis spectra between 400 nm and 800 nm were calculated and compared with the ZPL intensities. The results show a strong positive correlation between the slopes of the absorption spectra and the ZPL intensities of PL spectra at 637 nm. Therefore, this paper demonstrates the feasibility of estimating the concentration of the NV centers from measuring the transmission UV-Vis spectrum.
The nitrogen-vacancy (NV) center in diamond enables optical initialization and readout of its electronic spin, forming the basis of a wide range of quantum sensing and metrology applications. A central challenge in such measurements is the coexistence of two charge states, NV- and NV0: While detection protocols rely on the spin-dependent properties of NV-, fluorescence from NV0 does not carry useful contrast and is typically removed as background, reducing the available signal. Here, we show that the origin of NV0 emission depends strongly on the excitation wavelength in nitrogen-containing diamond. Using ensembles of NV centers with varying nitrogen concentrations, we compare excitation at the NV0 zero-phonon line (ZPL) at 575 nm with the commonly used 532 nm. We find that excitation at 575 nm generates NV0 predominantly through spin-selective tunneling from the excited state of NV- to nearby nitrogen donors, such that the NV0 emission follows the spin polarization of NV-. As a result, the NV0 fluorescence contributes to the measurable spin contrast, allowing the full fluorescence signal to be used for detection. This result opens opportunities for improved sensitivity in NV-based sensing applications.
Characterizing nitrogen-vacancy (NV) ensembles requires connecting their collective spectra to individual centers that experience different local environments. We develop a symbolic-regression pipeline that carries single-center spin structure into a calibrated ensemble model by generating individual spectral responses and combining them with explicit weights. A constrained search selects Hermitian operator terms from single-center optically detected magnetic resonance spectra, fits their coefficients, and retains the selected expressions as source models for the ensemble. Ensemble calibration then accounts for resonance shifts, local disorder, orientation, and optical response while keeping the individual spectral contributions accessible. On public single-center and ensemble data, the zero-field ensemble held-frequency root-mean-square error decreases from 0.008835 to 0.003872 in normalized photoluminescence, a 56.2% improvement over matched uncorrected composition. In controlled QuTiP ensembles of 128 sites spanning four NV orientations, models calibrated at 0 and 3 mT predict an independently held-out 5.17 mT spectrum with errors of 0.000207-0.000228 across three random seeds, comparable to the 0.000200 noise standard deviation. Resolving the simulated response into its individual-center contributions shows how local spectral diversity combines into the ensemble line shape. By retaining the source Hamiltonians while calibrating sample-dependent spectral differences, the pipeline connects local spin physics to collective optical readout and makes the contributions to an ensemble line shape available for physical interpretation.