A time-resolved Raman spectrometer is demonstrated based on a 256×8 CMOS SPAD line sensor and a 573 nm fiber-coupled diamond Raman laser delivering pulses with duration below 100 ps FWHM. The collected back scattered light from the sample is dispersed on the line sensor using a custom volume holographic grating having 1800 lines/mm. Efficient fluorescence rejection in the Raman measurements is achieved due to a combination of time gating on sub-100 ps-time scale and a 573 nm excitation wavelength. To demonstrate the performance of the spectrometer, fluorescent oil samples were measured. For organic sesame seed oil having a continuous wave mode fluorescence-to-Raman ratio of 10.5 and a fluorescence lifetime of 2.7 ns, a signal-to-distortion value of 76.2 was achieved. For roasted sesame seed oil having a continuous wave mode fluorescence-to-Raman ratio of 82 and a fluorescence lifetime of 2.2 ns, a signal-to-distortion value of 28.2 was achieved. In both cases, the fluorescence-to-Raman ratio was reduced by a factor of 24-25 owing to time gating. For organic oil, spectral distortion was dominated by dark counts while for the more fluorescent roasted oil, the main source of spectral distortion was timing skew of the sensor. With the presented post-processing techniques, the level of distortion could be reduced by 88-89 % for both samples. Compared to common 532 nm excitation, approximately 73 % lower fluorescence-to-Raman ratio was observed for 573 nm excitation when analyzing the organic sesame seed oil. Index Terms-Fluorescence rejection, Raman laser, Raman spectrometer, Raman spectroscopy, SPAD sensor, time-correlated single photon counting, time gating, timing skew I. INTRODUCTION AMAN spectroscopy is used in a wide range of fields including food and oil industries, mining industry, medical diagnostics, pharmacy, forensic science and archaeometry [1]
The fluorescence background in Raman spectroscopy can be effectively suppressed by using pulsed lasers and time-gated detectors. A recent solution to reduce the high complexity and bulkiness of the time-gated systems is to implement the detector by utilizing time-resolved single-photon avalanche diodes (SPADs) fabricated in complementary-metal-oxide-semiconductor (CMOS) technology. In this study, we investigate the effects of fluorescenceto-Raman ratio, recording time and excitation intensity on the quality of Raman spectra measured by using one of the furthest developed fluorescence-suppressed Raman spectrometers based on a time-resolved CMOS SPAD line sensor. The objectives were to provide information on the significance of the different causes behind the distortion of the measured Raman spectra with various measurement conditions and to provide general information on the possibilities to exploit the high-intensity non-stationary pulsed laser excitation to gain additional improvement on the spectral quality due to laser-induced fluorescence saturation. It was shown that the distortion of the spectra with samples having short fluorescence lifetimes (∼2 ns) and high fluorescence-to-Raman ratios, i.e. with challenging samples, is dominated by the timing skew of the sensor instead of the shot noise caused by the detected events. In addition, the actual reason for the observed improvement in the spectral quality as a function of excitation intensity was discovered not to be the conventionally thought increased number of detected photons but rather the laser-induced fluorescence saturation. At best, 26% improvement to the signal-to-noise ratio was observed due to fluorescence saturation.
Two methods were developed to compensate for the timing skew of CMOS SPAD line sensors used for time-resolving Raman spectroscopy. Both methods were tested using a timeresolving Raman spectrometer built around a 256-channel CMOS SPAD line sensor. As an example, Raman spectrum of highly fluorescent sesame seed oil was measured. Most of the distortion in the measured spectrum was caused by the timing skew and about 75 % of it could be removed by using either of the methods presented.
A 256-channel single-photon avalanche diode (SPAD) line sensor was designed for time-resolved Raman spectroscopy in 110-nm CMOS technology. The line sensor consists of an 8 × 256 SPAD array and 256 parallel connected time-todigital converters (TDCs). The adjustable temporal resolution and dynamic range of TDCs are 25.6-65 ps and 3.2-8.2 ns, respectively. The median timing skew along 256 channels is 43.7 ps, and TDC bin boundaries can be fine-tuned at the ps-level to enable precise timing skew compensation. The sensor is capable of real-time dark count measurement (two dark measurements for each excitation pulse) that gives accurate data for dark count compensation without any increment in measurement time. The maximum excitation pulse rate with realtime dark count measurement is 680 kHz. Raman spectra of six different samples were measured to prove the performance of the sensor in time-resolved Raman spectroscopy.
Single-Photon Avalanche Photodiodes (SPADs) were fabricated and characterized in 150 nm CMOS technology. The SPAD is based on a p+/nwell junction with a p-substrate guard ring. In addition, a compact gain switched quantum well (QW) laser diode with a CMOS driver was used with the proposed SPAD for time-resolved diffuse optics measurements. The measured impulse response function (IRF) of the SPADs was ~50 ps at best. Two phantoms were measured to demonstrate the suitability of SPADs for time-resolved diffuse optics imaging (TRDOI).
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