Elimination of scattering effects in spectral measurement of granulated materials using terahertz pulsed spectroscopy Y. C. Shen, 1,a P. F. Taday, 2 and M. Pepper 2 1 Department of Electrical Engineering and Electronics, University of Liverpool, Liverpool L69 3GJ, United Kingdom 2 TeraView Limited, Platinum Building, St John’s Innovation Park, Cambridge CB4 0WS, United Kingdom Received 12 December 2007; accepted 15 January 2008; published online 5 February 2008 Spectral distortions are commonly observed in terahertz spectra of granulated materials. These spurious structures in the spectroscopy are caused by scattering due to the refractive index mismatch between the particles and their surrounding medium. We find that the scattering contribution is random across sample positions and could be eliminated by summing and averaging multiple measurements over a sample area. We present experimental results of both absorbing and nonabsorbing particles in the size range 50–250 m and also give an empirical expres- sion to describe the effect of grain size on the scattering-induced extinction as a function of frequency. © 2008 American Institute of Physics. DOI: 10.1063/1.2840719 The terahertz region of the electromagnetic spectrum spans the frequency range between the midinfrared and the millimeter/microwave. The relatively unexplored central part of the region 0.3–3 THz or 10–100 cm -1 comprises fre- quencies lower than those corresponding to most internal vibrations of isolated small molecules. Instead, spectra con- tain information on motions associated with coherent, delocalized movements of large numbers of atoms and molecules. 1 The newly developed technique of terahertz pulsed spectroscopy TPShas been demonstrated to be a powerful tool for studying these low-frequency vibrational modes. 24 A major advantage of TPS is that the transient electric field, not simply the intensity of the terahertz radia- tion, is measured. This coherent detection scheme not only yields terahertz spectra with excellent signal-to-noise ratio and high dynamic range but also allows both the absorption coefficient and refractive index to be obtained without the need for Kramers–Kronig dispersion relationship. 2 Owing to these advantages, TPS is being widely used in studying low- frequency vibrational modes for a wide variety of samples including chemical, biological, pharmaceutical, and security- related materials. 510 In most of the work reported so far, TPS measurements were performed on solid crystalline sample powderin the form of pellet. Therefore, it is essen- tial to investigate the scattering of terahertz radiation by par- ticles presented in the sample and, in particular, the practical ways to minimize the scattering effect for getting reliable terahertz spectra of granulated materials. The propagation of terahertz pulses in random media comprising many 800-m-diameter Teflon spheres has been studied previously, 11 and the scattering of terahertz pulses by individual spheres or cylinders has also been measured. 12 These novel studies utilized the unique capabilities of TPS for characterizing the scattered electric field with unprecedented spatial and temporal resolution, leading to further insight into the scattering phenomena. 1315 In a recent Food and Drug Administration FDAstudy, Wu et al. 16 measured terahertz spectra of a number of granulated phar- maceutical materials with grain size comparable to terahertz wavelength and found that the particle scattering becomes significant at higher terahertz frequencies. Very recently, Zurk et al. 17 measured terahertz scattering of granular mate- rials polyethylene particles with two different grain sizes and explained the observed scattering response using the dense medium theory. In this paper, we study the effect of particle scattering on TPS spectrum in the frequency range 0.3–3 THz 10–100 cm -1 for both absorbing and nonab- sorbing particles in the size range 50– 250 m. We find that the scattering contribution could be eliminated by either a novel procedure of summing and averaging over a mapped area or, where this is possible, a traditional procedure of proper sample preparation. The nonabsorbing material used is the high-density poly- ethylene PEpowder Inducos 13 / 1 and 13 / 3, with particle sizes 80 and 50–200 m, respectivelyInduchem AG, Switzerland. The PE particles in these samples were further size fractionated using test sieves Endecotts Ltd, UKinto six size categories: 53 m, 50–75, 75–80, 75–106, 106– 150, and 150–200 m. PE is nearly transparent with a frequency-independent index of refraction of 1.53 in tera- hertz region. 9 Sucrose was used as an absorbing material. Granulated sucrose the coarse grain size up to 800 mwas first crushed to a coarse powder using pestle and mortar, and then milled using a Specamill Specac Ltd, UK, and finally size fractionated into five size categories: 52, 53–75, 75– 106, 106–150, and 150–250 m. For TPS measurements, the particles were contained in a specially designed powder cell with a volume of 0.53 cm 3 composed of two 3-mm-thick PE windows separated by a 3-mm-thick spacer. In all TPS measurements, the cell was filled with either 300 mg PE powder or 60 mg sucrose diluted in 260 mg PE particle size 53 m. The filling factor, which is defined by the ratio of the sample volume to the cell volume, was estimated to be 0.6 0.04 for above powder samples. The experimental setup and operating principle for TPS have been well documented. 24 In our experiments, we used a TPS spectra 1000 transmission spectrometer TeraView Limited, UK. Measurements were performed in rapid scan mode at a rate of 30 scans / second, providing a useful spec- tral range 0.2–3.0 THz 6–100 cm -1 with a spectral reso- lution of 40 GHz 1.3 cm -1 . For each sample or reference empty powder cellmeasurement, the terahertz waveform a Electronic mail: y.c.shen@liv.ac.uk. APPLIED PHYSICS LETTERS 92, 051103 2008 0003-6951/2008/925/051103/3/$23.00 © 2008 American Institute of Physics 92, 051103-1 Author complimentary copy. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp