A Raman spectrometer technique is described that aims at suppressing the fluorescence background typical of Raman spectra. The sample is excited with a high power (65W), short (300ps) laser pulse and the time position of each of the Raman scattered photons with respect to the excitation is measured with a CMOS SPAD detector and an accurate time-to-digital converter at each spectral point. It is shown by means of measurements performed on an olive oil sample that the fluorescence background can be greatly suppressed if the sample response is recorded only for photons coinciding with the laser pulse. A further correction in the residual fluorescence baseline can be achieved using the measured fluorescence tails at each of the spectral points.

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A 16 × 256 element single-photon avalanche diode array with a 256-channel, 3-bit on-chip time-to-digital converter (TDC) has been developed for fluorescence-suppressed Raman spectroscopy. The circuit is fabricated in 0.35 µm highvoltage CMOS technology and it allows a measurement rate of 400 kframe/s. In order to be able to separate the Raman and fluorescence photons even in the presence of the unavoidable timing skew of the timing signals of the TDC, the time-of-arrival of every detected photon is recorded with high time resolution at each spectral point with respect to the emitted short and intensive laser pulse (∼150 ps). The dynamic range of the TDC is set so that no Raman photon is lost due to the timing skew, and thus the complete time history of the detected photons is available at each spectral point. The resolution of the TDC was designed to be adjustable from 50 ps to 100 ps. The error caused by the timing skew and the residual variation in the resolution of the TDC along the spectral points is mitigated utilizing a calibration measurement from reference sample with known smooth fluorescence spectrum. As a proof of concept, the Raman spectrum of sesame seed oil, having a high fluorescence-to-Raman ratio and a short fluorescence lifetime of 1.9 ns, was successfully recorded.

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