Anomalous Enhancement of the Surface IR Modes in Photoacoustic Spectroscopy of SiO Particles

"A comparative study of the intensities of the IR modes in the pjlotoacoustic and. FrIR spectroscopy of amorphous and crystalline SiO2 particles is presented. It is observed that in photoacoustic spectroscopy of amorphous SiO2, IR modes of surface species are enhanced by over an order of magnitude compared to the bulk IR modes of SiO2. This effect, though not yet understood, may find applications in surface science.Since the publication of the Rosencwaig-Gersho theory of the photoacoustic effect in solids in 1976 [1], a great deal of attention has been paid to the development .of photoacoustic spectroscopy (PAS) into an analytical technique for condensed matter studies, especially when combined with the modern Fourier transform infrared (FTIR) spectrometer [2-8]. PAS has now been applied to a variety of experimental situations [2, 3] and it is particularly suitable for opaque powders and for cases where ~ample preparation (e.g. mixing with KBr as is usually done in FTIR spectroscopy) is not desirable. Another area of interest is the depth profiling feature of PAS, which is studied by varying the modulation frequency of the incident radiation [2-8]. The one-dimensional Rosencwaig-Gersho theory for non-porous samples has been extended to other cases [9-12]. Recently it has become known [11, 12] that for porous samples with porosity the IR modes are enhanced by a factor proportional toe. This enhancement is due to the pressure wave set up in the interstitial gas in the porous sample and this enhancement has been reported by a number of groups [12-14].In this Letter we report the observation of anomalously large enhancement of the PAS signal for certain surface IR modes on the surface of amorphous silica particles. This observation differs from the previous reports in that certain surface modes are enhanced by over an order of magnitude compared to the bulk IR modes. Although the reasons for this enhancement of the surface IR modes in PAS are not understood at present, this observation may open up new approaches to the study of surfaces. Results of these initial observations are given in this Letter. ·Experimental studies reported here were carried out on an FTIR spectrometer (Mattson Instruments, Model Cygnus 100) equipped with an MCT detector. The same instrument was used for PAS studies in conjunction with an MTEC (Model 100) PA cell. The sample cell and the spectrometer are continuously flushed with dry, CO2 free air obtained by the use of Balston Instruments Air Dryer Filter System (Model 75-60). Usually data were collected for 32 scans at 4 cm-I resolution, although both scan and resolution can be varied. For FTIR studies, samples were mixed with IR-grade KBr and pelletised. For PAS, no sample preparation is necessary and data are ratioed against dry carbon black [4, 5]."